MDCAT full mock (all subjects) key facts
Every chapter of MDCAT full mock (all subjects) on one page: the 735 key facts, definitions and facts to remember, in syllabus order. Use it for a last look before a test, then check yourself.
Biology · Acellular life
Viruses: structure and classification
- Virion = one complete infective virus particle; nucleocapsid = capsid + the nucleic acid inside it
- Size: about 20 nm to 250 nm, so viruses pass through filters that hold back bacteria
- Capsid symmetry: helical (tobacco mosaic virus), polyhedral or icosahedral with 20 faces (poliovirus, adenovirus), complex (T4 bacteriophage: polyhedral head + tail)
- By host: bacteriophages infect bacteria, plant viruses infect plants, animal viruses infect animals
- DNA viruses: smallpox, herpes, hepatitis B, T4 phage. RNA viruses: polio, influenza, measles, mumps, HIV, tobacco mosaic virus
- Enveloped viruses: influenza, HIV, herpes. Naked (no envelope): poliovirus, tobacco mosaic virus, T4 phage
- T4 phage: head holds DNA; tail fibres attach to receptor sites on the bacterial wall
Viral replication and disease
- Lytic cycle order: attachment (adsorption) → penetration → replication of phage DNA and proteins → assembly → lysis
- Only the phage DNA enters the bacterium; the protein coat stays outside. Lysozyme from the phage tail makes the hole in the wall
- Virulent phage = lytic cycle only; temperate phage (for example lambda) = can follow either cycle
- Prophage = phage DNA inserted in the bacterial chromosome; the bacterium carrying it is lysogenic
- HIV in a helper T cell: attachment to the CD4 receptor → reverse transcription (RNA → DNA) → integration as a provirus → transcription and translation → assembly → budding
- HIV spreads by unprotected sexual contact, infected blood or shared needles, and from mother to child (placenta, birth, breast milk). It does not spread by touch, food, coughing or mosquitoes
- Prevention: screened blood, sterile needles, safe sexual behaviour, treatment of infected mothers. There is no cure and no vaccine; antiretroviral drugs slow the virus
Biology · Bioenergetics
Photosynthesis
- 6CO2 + 12H2O + light → C6H12O6 + 6O2 + 6H2O; the oxygen released comes from water
- Chlorophyll absorbs mainly violet-blue and orange-red light and reflects green. Absorption spectrum = light absorbed at each wavelength; action spectrum = rate of photosynthesis at each wavelength
- Photolysis: 2H2O → 4H+ + 4e− + O2, at photosystem II (P680)
- Non-cyclic photophosphorylation: both photosystems; electrons go water → PS II → PS I → NADP+; products ATP, NADPH and O2
- Cyclic photophosphorylation: photosystem I (P700) only; electrons return to P700; product ATP only
- Calvin cycle: carbon fixation (CO2 + RuBP → two 3-carbon PGA, enzyme RuBisCO) → reduction (PGA → G3P, uses ATP and NADPH) → regeneration of RuBP (uses ATP)
- Each CO2 fixed uses 3 ATP and 2 NADPH. Limiting factors: light intensity, CO2 concentration, temperature, water
Cellular respiration
- C6H12O6 + 6O2 → 6CO2 + 6H2O + energy (ATP)
- Glycolysis: glucose (6C) → 2 pyruvic acid (3C); 2 ATP used, 4 made, net 2 ATP; 2 NADH; no CO2; no oxygen needed
- Link reaction (per pyruvic acid): pyruvic acid → acetyl CoA (2C) + CO2 + NADH
- Krebs cycle (per turn): 2 CO2, 3 NADH, 1 FADH2, 1 ATP; oxaloacetic acid (4C) is regenerated; two turns per glucose
- Electron transport chain: each NADH gives 3 ATP, each FADH2 gives 2 ATP; H+ is pumped into the intermembrane space and flows back through ATP synthase; oxygen is the final electron acceptor
- Per glucose: 10 NADH (30 ATP) + 2 FADH2 (4 ATP) + 4 ATP made directly = 38 ATP; 36 ATP in most eukaryotic cells, because 2 ATP are spent moving the NADH of glycolysis into the mitochondrion
- Anaerobic: yeast, pyruvic acid → acetaldehyde + CO2 → ethanol; muscle, pyruvic acid → lactic acid. Fats enter as acetyl CoA; amino acids are deaminated first
Biology · Biological molecules
Water and carbohydrates
- High specific heat capacity: keeps body and lake temperatures steady. High heat of vaporisation: sweating and transpiration cool. Ice is less dense than water, so it floats
- Monosaccharides by carbon number: triose 3C (glyceraldehyde), pentose 5C (ribose, deoxyribose, ribulose), hexose 6C (glucose, fructose, galactose). Aldose = aldehyde group (glucose); ketose = ketone group (fructose)
- Maltose = glucose + glucose; sucrose = glucose + fructose; lactose = glucose + galactose
- Starch = amylose (unbranched, α 1→4) + amylopectin (branched, α 1→4 and α 1→6): plant store
- Glycogen: α-glucose, more branched than amylopectin: animal store in liver and muscle
- Cellulose: β-glucose, β 1→4, straight unbranched chains: plant cell walls
- Iodine test: starch blue-black, glycogen red-brown, cellulose no colour. n monosaccharides in a chain have (n − 1) glycosidic bonds
Proteins and lipids
- About 20 kinds of amino acid occur in proteins; glycine is the simplest (R = H). A chain of n amino acids has (n − 1) peptide bonds
- Primary structure = sequence of amino acids. Secondary = α-helix or β-pleated sheet held by hydrogen bonds
- Tertiary = 3-D folding of one chain (ionic bonds, hydrogen bonds, disulphide bridges between cysteines, hydrophobic interactions). Quaternary = two or more chains together (haemoglobin has four)
- Fibrous proteins: long, insoluble, structural (keratin, collagen, silk). Globular proteins: compact, soluble (enzymes, antibodies, haemoglobin)
- Triglyceride = 1 glycerol + 3 fatty acids, 3 ester bonds, 3 water molecules released
- Saturated fatty acid: no C=C, higher melting point (fats). Unsaturated: one or more C=C, lower melting point (oils)
- Other lipids: waxes (waterproofing), steroids such as cholesterol (four fused rings), terpenoids such as carotenoids (isoprene units). Fat stores about twice as much energy per gram as carbohydrate
Nucleic acids
- Purines (two rings): adenine, guanine. Pyrimidines (one ring): cytosine, thymine, uracil. Nucleoside = sugar + base; nucleotide = sugar + base + phosphate
- Base pairing: A=T with 2 hydrogen bonds, G≡C with 3. So A = T, G = C and (A + G) = (T + C)
- Double helix: 10 base pairs per turn, 3.4 nm per turn, 0.34 nm between base pairs, 2 nm wide; nucleotides in one strand joined by phosphodiester bonds
- Replication: helicase unwinds; primase makes an RNA primer; DNA polymerase III adds nucleotides 5′ → 3′; leading strand continuous, lagging strand in Okazaki fragments joined by DNA ligase
- Transcription: RNA polymerase copies the template strand into mRNA; mRNA has the same sequence as the coding strand with U in place of T
- Genetic code: 64 triplet codons; 61 code for amino acids, 3 are stop codons (UAA, UAG, UGA); AUG is the start codon (methionine)
- mRNA carries the code, tRNA carries amino acids and has the anticodon, rRNA builds ribosomes
Biology · Cell structure and function
Cell membrane and transport
- Diffusion: net movement from higher to lower concentration; passive; no protein needed
- Facilitated diffusion: down the gradient through a specific channel or carrier protein; passive; rate levels off when all carriers are in use
- Osmosis: net movement of water through a selectively permeable membrane from higher water potential (dilute solution) to lower water potential (concentrated solution)
- Water potential (ψ): pure water = 0; any solution is negative; more solute = more negative
- Active transport: against the gradient, carrier protein + ATP; sodium–potassium pump moves 3 Na+ out and 2 K+ in per ATP
- Endocytosis (into the cell): phagocytosis = solid particles, pinocytosis = fluid droplets. Exocytosis: vesicles fuse with the membrane and release their contents. Both need ATP
- Animal cell: bursts in a hypotonic solution, shrinks in a hypertonic one. Plant cell: turgid in hypotonic, plasmolysed in hypertonic
Organelles
- Nucleus: double membrane (envelope) with pores; chromatin = DNA + histone proteins; nucleolus makes rRNA and ribosome subunits
- Rough ER: ribosomes attached, makes and transports proteins. Smooth ER: no ribosomes, makes lipids and steroids, detoxifies drugs
- Ribosomes: no membrane; 80S (60S + 40S) in eukaryotic cytoplasm, 70S (50S + 30S) in prokaryotes, mitochondria and chloroplasts
- Golgi apparatus: receives vesicles at the forming (cis) face, adds carbohydrate to make glycoproteins, releases vesicles and lysosomes from the maturing (trans) face
- Lysosomes: single membrane, hydrolytic enzymes; digest food particles and worn-out organelles (autophagy)
- Mitochondrion: inner membrane folded into cristae, matrix inside. Chloroplast: thylakoids stacked into grana, stroma around them
- Microtubules (tubulin): spindle, cilia, centrioles (9 triplets). Microfilaments (actin): cyclosis, amoeboid movement. Plant vacuole is bounded by the tonoplast; plant cell wall is cellulose and fully permeable
Prokaryotic and eukaryotic cells
- Prokaryote: 70S ribosomes, wall of peptidoglycan (murein), circular DNA without histones, no mitochondria (respiratory enzymes on the plasma membrane), divides by binary fission
- Eukaryote: 80S ribosomes in the cytoplasm, linear DNA with histones in a nucleus, membrane-bound organelles, divides by mitosis or meiosis
- Typical size: prokaryotic cell about 1 to 10 μm; eukaryotic cell about 10 to 100 μm
- Plant cell only: cellulose wall, chloroplasts and other plastids, large central vacuole. Animal cell only: centrioles; stores glycogen, not starch
- magnification = image size ÷ actual size; 1 mm = 1000 μm; 1 μm = 1000 nm
- Light microscope: lower resolution, can view living cells. Electron microscope: resolution to below 1 nm, specimen dead and in a vacuum; TEM shows internal detail, SEM shows 3-D surfaces
- Structure fits function: sperm has many mitochondria for movement; red blood cell has no nucleus, more room for haemoglobin; root hair has a large surface area
Biology · Coordination and control
Neurons and the nerve impulse
- Resting potential: sodium–potassium pump moves 3 Na+ out and 2 K+ in; the membrane leaks K+ out far more easily than Na+ in; large negative ions stay inside
- Depolarisation = Na+ diffuses in. Repolarisation = K+ diffuses out. The pump then restores the original ion balance
- All-or-none: below threshold there is no impulse; above it every impulse has the same size. A stronger stimulus gives more impulses per second, not bigger ones
- Myelin sheath (Schwann cells) insulates the axon; the impulse jumps between nodes of Ranvier (saltatory conduction), up to about 100 m s−1
- Synapse: impulse arrives → Ca2+ enters the synaptic knob → vesicles release neurotransmitter → it diffuses across the cleft → binds receptors on the postsynaptic membrane → new impulse
- Acetylcholine is broken down by acetylcholinesterase. A synapse passes impulses in one direction only
- Sensory neuron cell bodies lie in the dorsal root ganglion; Nissl's granules are groups of ribosomes in the cell body
The nervous system
- Cerebrum (cerebral cortex): thinking, memory, intelligence, voluntary movement, senses. Each hemisphere controls the opposite side of the body; the corpus callosum joins the two
- Thalamus: relays sensory impulses to the cortex. Hypothalamus: temperature, hunger, thirst, controls the pituitary. Amygdala and hippocampus: emotion and memory
- Cerebellum: balance, posture, coordination of movement. Medulla oblongata: breathing, heartbeat, blood pressure. Pons: links cerebellum, medulla and cerebrum
- Spinal cord: grey matter (cell bodies) inside in an H shape, white matter (myelinated axons) outside; the cerebrum has grey matter outside
- Reflex arc: receptor → sensory neuron (dorsal root) → interneuron in the spinal cord → motor neuron (ventral root) → effector
- Sympathetic system: prepares for emergency (faster heart, dilated pupils, slower digestion). Parasympathetic: rest (slower heart, constricted pupils, active digestion)
- Receptors: chemoreceptors (taste, smell), mechanoreceptors (touch, pressure, hearing), photoreceptors (light), thermoreceptors (temperature), nociceptors (pain). Disorders: Parkinson's (low dopamine, tremor), epilepsy (seizures), Alzheimer's (loss of memory)
Chemical coordination
- Anterior pituitary: growth hormone, TSH (thyroid), ACTH (adrenal cortex), FSH, LH, prolactin (milk production). Posterior pituitary releases ADH (water reabsorption in the kidney) and oxytocin (labour, milk ejection), both made in the hypothalamus
- Thyroid: thyroxine raises metabolic rate and needs iodine; calcitonin lowers blood Ca2+. Parathyroid: parathormone raises blood Ca2+
- Pancreas (islets of Langerhans): β cells, insulin lowers blood glucose (glucose → glycogen); α cells, glucagon raises it (glycogen → glucose)
- Adrenal medulla: adrenaline and noradrenaline (emergency). Adrenal cortex: cortisol (raises blood glucose in stress), aldosterone (Na+ reabsorption)
- Gonads: testosterone (testes); oestrogen and progesterone (ovaries)
- Growth hormone: too little in childhood = dwarfism; too much in childhood = gigantism; too much in adults = acromegaly
- Thyroxine: too little = cretinism (child), myxoedema (adult); too much = Graves' disease. Insulin lack = diabetes mellitus; ADH lack = diabetes insipidus; cortex hormones low = Addison's, high = Cushing's
Biology · Enzymes
Enzyme action
- Activation energy = energy of the peak − energy of the reactants. An enzyme lowers the peak only.
- Lock-and-key model (Fischer): the active site is rigid and the substrate (key) fits it exactly.
- Induced-fit model (Koshland): the active site changes shape slightly as the substrate binds, to fit it closely.
- Holoenzyme (active) = apoenzyme (protein part) + cofactor (non-protein part).
- Activator: a detachable inorganic ion, e.g. Mg2+, Cl−.
- Coenzyme: an organic cofactor that is loosely attached, e.g. NAD, FAD; many are made from vitamins.
- Prosthetic group: a non-protein part bound tightly (covalently) to the protein, e.g. haem.
Factors and inhibition
- Enzyme concentration: with excess substrate, rate is directly proportional to the amount of enzyme.
- Substrate concentration: rate rises, then levels off at a maximum when every active site is occupied (saturation).
- Optimum pH: pepsin about 2, salivary amylase about 6.8, pancreatic lipase about 9.
- Competitive inhibitor: resembles the substrate and binds at the active site; more substrate overcomes it, so the maximum rate is still reached.
- Non-competitive inhibitor: binds at another site and changes the shape of the active site; more substrate does not help, so the maximum rate is lower.
- Irreversible inhibitors (e.g. cyanide) bind by strong covalent bonds; the enzyme stays inactive.
- Feedback inhibition: the end product of a pathway slows an early enzyme of that pathway.
Biology · Evolution
Theories of evolution
- Lamarck: use and disuse of organs, and inheritance of acquired characters.
- Darwin: overproduction → struggle for existence → variation → survival of the fittest → inheritance of the favoured variations.
- Darwin published 'On the Origin of Species' in 1859; Malthus gave him the idea that populations outgrow their food supply.
- Fitness means leaving the most offspring that survive to breed, not being the strongest.
- Mutation is the only source of new alleles; crossing over and independent assortment only make new combinations.
- Only mutations in germ cells (which form gametes) can be inherited.
- Hardy-Weinberg: allele frequencies stay constant if the population is large, mates at random and has no mutation, migration or selection.
Evidence and speciation
- Fossils: in undisturbed sedimentary rock, deeper layers are older. Archaeopteryx links reptiles and birds.
- Homologous organs: same basic structure and origin, different function (human arm, bat wing, whale flipper); show divergent evolution from a common ancestor.
- Analogous organs: same function, different structure and origin (bird wing, insect wing); show convergent evolution.
- Vestigial organs: reduced and no longer used for their original function, e.g. coccyx, appendix.
- Embryology: early vertebrate embryos all have gill pouches and a tail.
- Biochemistry: the fewer the differences in a protein or in DNA, the more recent the common ancestor.
- Adaptive radiation: one ancestor gives many species suited to different ways of life, e.g. Galápagos finches.
Biology · Reproduction
Human reproductive systems
- Spermatogonium (2n) → primary spermatocyte (2n) → 2 secondary spermatocytes (n) → 4 spermatids (n) → 4 sperm.
- Oogonium (2n) → primary oocyte (2n) → secondary oocyte (n) + first polar body → ovum (n) + second polar body.
- One primary spermatocyte gives 4 sperm; one primary oocyte gives 1 ovum.
- Primary oocytes are held at prophase I from before birth; meiosis II is completed only after a sperm enters.
- Spermatogenesis begins at puberty and is continuous; oogenesis begins before birth and ends at menopause.
- In the male, FSH promotes spermatogenesis; LH stimulates the interstitial cells to secrete testosterone.
- Seminal vesicles secrete fructose, the energy source of sperm.
Reproductive cycle and development
- Order of events: menstruation (days 1 to 5) → follicle growth and oestrogen → LH surge and ovulation (about day 14) → corpus luteum and progesterone.
- Oestrogen and progesterone inhibit FSH and LH (negative feedback); this is how the contraceptive pill prevents ovulation.
- hCG from the embryo keeps the corpus luteum alive in early pregnancy; later the placenta makes the progesterone.
- Cleavage is mitosis with little growth: zygote → morula → blastocyst, which implants.
- Germ layers: ectoderm → nervous system and epidermis; mesoderm → muscle, skeleton, blood; endoderm → lining of gut and lungs.
- Placenta: maternal and foetal blood do not mix. The umbilical cord has two arteries (deoxygenated blood to the placenta) and one vein.
- STDs: gonorrhoea (Neisseria gonorrhoeae), syphilis (Treponema pallidum), AIDS (HIV), genital herpes (herpes simplex virus).
Biology · Support and movement
Skeleton and joints
- Vertebrae: 7 cervical, 12 thoracic, 5 lumbar, then the sacrum (5 fused) and coccyx (4 fused). Ribs: 12 pairs.
- Bone cells: osteoblasts build bone, osteocytes maintain it, osteoclasts dissolve it and release calcium.
- Cartilage: hyaline (ends of bones, nose, trachea), elastic (pinna, epiglottis), fibrocartilage (intervertebral discs, pubic symphysis).
- Joints: fibrous, immovable (skull sutures); cartilaginous, slightly movable (between vertebrae); synovial, freely movable.
- Synovial types: hinge (elbow, knee), ball and socket (shoulder, hip), pivot (atlas and axis).
- Osteoarthritis: articular cartilage wears away with age. Rheumatoid arthritis: the immune system attacks the joint lining.
- Osteoporosis: loss of bone mass, so bones become porous and break easily; common after menopause as oestrogen falls.
Muscles and contraction
- A band = full length of the myosin filaments (dark); I band = actin only (light); H zone = myosin only, in the middle of the A band.
- On contraction the A band stays the same; the I band and H zone get shorter; Z lines move closer.
- Ca2+ is released from the sarcoplasmic reticulum, binds troponin, and tropomyosin moves off the binding sites on actin.
- Myosin heads are ATPases. ATP is needed for the head to detach from actin; without ATP the muscle stays stiff (rigor mortis).
- Skeletal: striated, voluntary, many nuclei, unbranched. Cardiac: striated, involuntary, branched, with intercalated discs.
- Smooth: unstriated, involuntary, spindle-shaped cells with one nucleus; found in the gut and blood vessels.
- Tendon joins muscle to bone; ligament joins bone to bone. Origin is the fixed end, insertion the moving end.
Biology · Inheritance
Mendelian inheritance
- Monohybrid cross Aa × Aa: genotypes 1 AA : 2 Aa : 1 aa; phenotypes 3 dominant : 1 recessive.
- Test cross: unknown dominant phenotype × homozygous recessive. All dominant offspring → parent is AA; 1 : 1 → parent is Aa.
- Dihybrid cross AaBb × AaBb: phenotypes 9 : 3 : 3 : 1 (out of 16).
- Dihybrid test cross AaBb × aabb: 1 : 1 : 1 : 1.
- Number of kinds of gamete = 2n, where n is the number of heterozygous gene pairs.
- For independent genes, multiply the separate probabilities (product rule).
Beyond simple dominance
- Incomplete dominance, heterozygote × heterozygote: 1 : 2 : 1 for both phenotype and genotype.
- ABO: IA and IB are codominant and both are dominant to i. Group A = IAIA or IAi; B = IBIB or IBi; AB = IAIB; O = ii.
- Three alleles give 6 genotypes and 4 phenotypes.
- Group O has no A or B antigens (universal donor of red cells); group AB has no anti-A or anti-B antibodies (universal recipient).
- Epistasis changes 9 : 3 : 3 : 1 to 9 : 3 : 4 (recessive epistasis) or 12 : 3 : 1 (dominant epistasis).
- Rh factor: Rh-positive (D) is dominant to Rh-negative (d).
- Haemolytic disease of the newborn: Rh-negative mother, Rh-positive foetus, usually in a second or later such pregnancy.
Sex linkage and chromosomes
- A father gives his X to all his daughters and his Y to all his sons; a son's X always comes from his mother.
- Carrier mother × normal father: half the sons affected, half the daughters carriers, no daughter affected.
- Affected father × normal (non-carrier) mother: all daughters carriers, all sons normal.
- Haemophilia A is a lack of clotting factor VIII.
- Down syndrome: trisomy 21, 47 chromosomes. Turner syndrome: 45, XO, a sterile female. Klinefelter syndrome: 47, XXY, a sterile male.
- In humans the presence of a Y chromosome gives a male.
- Other systems: XO in grasshoppers (male has one X only); ZW in birds (the female is ZW and decides the sex).
Biology · Circulation
The heart
- Path: venae cavae → right atrium → tricuspid valve → right ventricle → pulmonary artery → lungs → pulmonary veins → left atrium → bicuspid (mitral) valve → left ventricle → aorta.
- The pulmonary artery carries deoxygenated blood; the pulmonary veins carry oxygenated blood.
- Impulse: SA node → AV node (short delay) → bundle of His → Purkinje fibres → ventricles contract from the apex upwards.
- Cardiac cycle at 75 beats per minute = 60 ÷ 75 = 0.8 s: atrial systole 0.1 s, ventricular systole 0.3 s, diastole of the whole heart 0.4 s.
- First sound 'lubb': the AV (tricuspid and bicuspid) valves close as the ventricles start to contract.
- Second sound 'dupp': the semilunar valves close as the ventricles start to relax.
- Sympathetic nerves speed up the SA node; the vagus (parasympathetic) nerve slows it.
Blood and blood vessels
- Normal resting blood pressure is about 120/80 mm Hg (systolic/diastolic).
- Blood flows slowest in the capillaries, because their total cross-sectional area is the greatest.
- Blood returns up the leg veins by the squeezing of skeletal muscles, with valves stopping backflow.
- Red blood cells: biconcave, no nucleus, carry oxygen on haemoglobin; made in red bone marrow; live about 120 days.
- White blood cells (about 7 000 to 8 000 per mm3): neutrophils (most common, phagocytes), lymphocytes (immunity), monocytes (largest, become macrophages), eosinophils (allergy, worms), basophils (heparin and histamine).
- Platelets are cell fragments that start clotting: prothrombin → thrombin (needs Ca2+); thrombin turns fibrinogen → fibrin.
- Plasma proteins: albumin (osmotic pressure), globulins (antibodies), fibrinogen (clotting).
Lymphatic system and disorders
- Net filtration pressure = blood (hydrostatic) pressure − osmotic pressure of the plasma
- Arterial end: hydrostatic pressure is greater, so fluid leaves. Venous end: osmotic pressure is greater, so fluid returns
- Lymph nodes filter lymph and hold lymphocytes and macrophages; lacteals in the villi absorb digested fats
- Oedema = swelling from excess tissue fluid (low plasma protein, blocked lymph vessels or high blood pressure)
- Atherosclerosis = cholesterol-rich plaque (atheroma) in the artery wall; arteriosclerosis = hardening of the wall, with calcium deposits
- Thrombus = a clot fixed where it formed; embolus = a clot or fragment carried in the blood
- Hypertension = blood pressure that stays at about 140/90 mm Hg or above; normal is about 120/80 mm Hg
Biology · Immunity
Innate and adaptive immunity
- Phagocytosis: attachment to the microbe → engulfing into a vacuole (phagosome) → lysosomes fuse with it → enzymes digest the microbe
- Inflammation: mast cells release histamine → arterioles dilate and capillaries become leaky → redness, heat, swelling and pain
- Interferon is released by virus-infected cells and makes neighbouring cells resist viruses
- B cells mature in the bone marrow; T cells are made in the bone marrow and mature in the thymus
- An activated B cell divides to form plasma cells (which secrete antibodies) and memory cells
- Helper T cells activate B cells and killer T cells; killer (cytotoxic) T cells destroy infected body cells
- Antibody = 2 heavy chains + 2 light chains joined by disulphide bonds; the variable regions at the tips form 2 antigen-binding sites
Types of immunity and vaccination
- Natural active: recovering from an infection. Artificial active: vaccination
- Natural passive: antibodies across the placenta or in breast milk (colostrum). Artificial passive: an injection of antiserum or antitoxin
- A vaccine may be a live weakened (attenuated) microbe, a killed microbe, a toxoid (harmless toxin) or a single antigen
- Primary response: slow start, small amount of antibody, short-lived. Secondary response: quick, much more antibody, long-lasting
- Allergy = an excessive response to a harmless antigen (allergen); mast cells release histamine
- Autoimmune disease = the immune system attacks the body's own tissues, e.g. rheumatoid arthritis, type 1 diabetes, multiple sclerosis
- Edward Jenner introduced the first vaccine, against smallpox, in 1796
Biology · Respiration
Respiratory system and breathing
- Inspiration (active): diaphragm contracts and flattens; external intercostal muscles contract, ribs move up and out; volume rises, pressure falls, air enters
- Quiet expiration (passive): diaphragm and external intercostals relax; elastic recoil of the lungs; volume falls, pressure rises, air leaves
- Forced expiration is active: internal intercostal muscles and abdominal muscles contract
- Trachea and bronchi have cartilage; bronchioles have none, only smooth muscle. Goblet cells make mucus and cilia sweep it up to the pharynx
- Tidal volume = air breathed in or out in one quiet breath, about 500 cm3 (0.5 dm3)
- Vital capacity = tidal volume + inspiratory reserve volume + expiratory reserve volume
- Total lung capacity = vital capacity + residual volume; minute volume = tidal volume × breathing rate
Gas transport and disorders
- Hb + 4O2 ⇌ Hb(O2)4 (oxyhaemoglobin); the oxygen dissociation curve is S-shaped (sigmoid)
- Bohr effect: more CO2 or lower pH shifts the curve to the right (higher temperature does the same), so haemoglobin gives up more oxygen
- CO2 transport: about 70% as hydrogencarbonate ions, most of the rest as carbaminohaemoglobin, a small amount dissolved in plasma
- In red cells: CO2 + H2O ⇌ H2CO3 ⇌ H+ + HCO3−, speeded up by carbonic anhydrase
- Chloride shift: HCO3− diffuses out of the red cell and Cl− moves in to keep the charges balanced
- Smoke: tar causes cancer and damages cilia; nicotine is addictive and raises heart rate and blood pressure; carbon monoxide cuts oxygen carriage
- Emphysema = alveolar walls break down, less surface; pneumonia = alveoli fill with fluid; tuberculosis = Mycobacterium tuberculosis, prevented by BCG vaccine
Biology · Digestion
Alimentary canal and enzymes
- Salivary amylase (salivary glands) and pancreatic amylase (pancreas): starch → maltose
- Pepsin (gastric glands; secreted as pepsinogen and activated by HCl): proteins → shorter polypeptides
- Trypsin (pancreas; secreted as trypsinogen and activated by enterokinase): proteins and polypeptides → smaller peptides
- Lipase (mainly pancreas): fats → fatty acids + glycerol
- Intestinal wall: maltase gives glucose; sucrase gives glucose + fructose; lactase gives glucose + galactose; peptidases give amino acids
- HCl kills microbes and activates pepsinogen; mucus protects the stomach wall; gastrin stimulates the release of gastric juice
- Bile is made in the liver and stored in the gall bladder; the colon absorbs water and its bacteria make vitamin K
Absorption, liver and disorders
- Glucose and amino acids: absorbed by diffusion and active transport (cells have many mitochondria) → blood capillaries → hepatic portal vein
- Fatty acids and glycerol → reformed into fats → lacteal → lymph; fat-soluble vitamins A, D, E and K are absorbed with fats and need bile
- Liver: makes bile, stores glucose as glycogen, deaminates excess amino acids and makes urea, detoxifies poisons, makes plasma proteins (albumin, fibrinogen, prothrombin), stores iron and vitamins
- Pancreas: exocrine part sends pancreatic juice into a duct; endocrine part (islets of Langerhans) sends insulin and glucagon into the blood
- Peptic ulcer = a sore where acid and pepsin erode the wall of the stomach or duodenum; often linked with Helicobacter pylori
- Dyspepsia = indigestion, with discomfort in the upper abdomen
- Food poisoning = illness from food carrying bacteria or their toxins, e.g. Salmonella, Campylobacter
Biology · Homeostasis
Osmoregulation and the kidney
- The afferent arteriole is wider than the efferent arteriole, so the blood pressure in the glomerulus is high
- Filtrate contains water, glucose, amino acids, salts and urea; blood cells and plasma proteins are too large to pass
- Proximal convoluted tubule: reabsorbs all the glucose and amino acids and most of the water and salts
- Descending limb of the loop is permeable to water; ascending limb moves salts out and is impermeable to water
- Less water in the blood → more ADH from the posterior pituitary → collecting ducts more permeable to water → small volume of concentrated urine
- Too little ADH = diabetes insipidus: large volumes of dilute urine with no glucose
- Kidney stones are mostly calcium oxalate (lithotripsy breaks them with shock waves); in kidney failure, dialysis removes urea by diffusion across a partially permeable membrane
Thermoregulation and excretion
- Too hot: vasodilation of skin arterioles, sweating (cooling by evaporation), hairs lie flat, lower metabolic rate
- Too cold: vasoconstriction of skin arterioles, shivering (heat from skeletal muscles), hairs raised to trap air, more thyroxine and adrenaline raise the metabolic rate
- Fever: pyrogens raise the set point of the hypothalamus
- Ammonia: very toxic, very soluble, needs most water; aquatic animals such as bony fishes (ammonotelic)
- Urea: less toxic, soluble, needs moderate water; mammals and adult amphibians (ureotelic)
- Uric acid: least toxic, almost insoluble, needs least water; birds, reptiles and insects (uricotelic)
- Urea cycle: ornithine → citrulline → arginine; arginase splits arginine into urea + ornithine. Overall: 2NH3 + CO2 → CO(NH2)2 + H2O
Biology · Biotechnology
Recombinant DNA techniques
- Restriction enzymes (restriction endonucleases) cut DNA at specific palindromic sites, e.g. EcoRI at 5′-GAATTC-3′, often leaving sticky ends
- DNA ligase seals the sugar-phosphate backbone and joins the gene to the vector
- Cloning steps: isolate the gene → cut gene and plasmid with the same enzyme → join with ligase → transform host cells → select (antibiotic resistance marker) → grow
- One PCR cycle: denaturation at about 94 °C → primer annealing at about 50 to 60 °C → extension by Taq polymerase at about 72 °C
- Number of DNA molecules after n PCR cycles = starting number × 2n
- Electrophoresis: DNA is negatively charged and moves towards the positive electrode; smaller fragments travel further
- Sanger sequencing uses dideoxynucleotides, which lack a 3′-OH group and so stop the growing chain
Applications of biotechnology
- Human insulin from recombinant bacteria treats diabetes mellitus; recombinant growth hormone treats pituitary dwarfism
- Hepatitis B vaccine is a viral surface protein made in yeast; it has no whole virus, so it cannot cause the disease
- Gene therapy of body (somatic) cells is not inherited, because the eggs and sperm still carry the faulty allele
- Bt crops carry a gene from Bacillus thuringiensis for a protein that kills insect larvae; golden rice makes beta-carotene, which the body turns into vitamin A
- DNA fingerprinting compares repeated non-coding sequences (VNTRs or STRs); only identical twins share a profile, and every band in a child comes from the mother or the father
- Reproductive cloning by nuclear transfer (Dolly, 1996): the clone is genetically identical to the animal that gave the nucleus
- Ethical issues include gene flow to wild plants, long-term safety of GM food, privacy of genetic data and the cloning of humans
Chemistry · Fundamental concepts of chemistry
The mole
- moles = mass ÷ molar mass (n = m/M)
- number of particles = moles × 6.02 × 1023
- volume of a gas at STP = moles × 22.4 dm3
- 1 amu = one-twelfth of the mass of one carbon-12 atom
- % of an element = (mass of that element in 1 mol ÷ molar mass) × 100
- Empirical formula: divide each % by the atomic mass, then divide every answer by the smallest one
- molecular formula = (empirical formula)n, where n = molar mass ÷ empirical formula mass
Stoichiometry
- Coefficients in a balanced equation = ratio of moles
- Route: mass → moles → mole ratio → moles → mass or gas volume
- For gases at the same temperature and pressure, the volume ratio = the mole ratio
- Limiting reagent: divide the moles of each reactant by its coefficient; the smallest answer shows the limiting reagent
- Theoretical yield is calculated from the limiting reagent only
- percentage yield = (actual yield ÷ theoretical yield) × 100
- Mass is conserved: total mass of reactants used = total mass of products formed
Chemistry · Atomic structure
Particles, photons and the Bohr model
- neutrons = A − Z; electrons = Z − charge on the ion (so a negative ion has extra electrons)
- relative atomic mass = sum of (isotope mass × % abundance) ÷ 100
- Charge-to-mass ratio (e/m): electron > proton > alpha particle; a neutron has no charge and is not deflected
- energy of a photon = Planck's constant × frequency (E = hf = hc/λ); wave number = 1/λ
- Electron jump: ΔE = E2 − E1 = hf
- Hydrogen series: Lyman (to n = 1) ultraviolet; Balmer (to n = 2) visible; Paschen, Brackett and Pfund infrared
- Bohr radius of orbit n = 0.529 Å × n2; 1 Å = 10−10 m = 100 pm; 1 nm = 10 Å
Orbitals and electronic configuration
- n (principal) = 1, 2, 3 … gives the shell, its size and energy; l (azimuthal) = 0 to n − 1 gives the shape: s = 0, p = 1, d = 2, f = 3
- m (magnetic) = −l to +l gives the orientation; s (spin) = +½ or −½
- A shell has n2 orbitals and holds up to 2n2 electrons
- Aufbau: fill the subshell with the lower (n + l) first; if equal, the lower n first. Order: 1s 2s 2p 3s 3p 4s 3d 4p 5s
- Pauli: no two electrons in an atom have all four quantum numbers the same, so two electrons in one orbital have opposite spins
- Hund: orbitals of equal energy are each filled singly, with parallel spins, before any pairing
- Exceptions: Cr is [Ar] 3d5 4s1 and Cu is [Ar] 3d10 4s1
Chemistry · Gases
Gas laws
- Boyle's law: at constant T, P1V1 = P2V2
- Charles's law: at constant P, V1/T1 = V2/T2 (T in K); the V against T line reaches zero volume at −273 °C
- Avogadro's law: at the same T and P, equal volumes of gases contain equal numbers of molecules (V ∝ n)
- PV = nRT; R = 0.0821 dm3 atm K−1 mol−1 = 8.314 J K−1 mol−1; density d = PM/RT
- Dalton's law: total pressure = sum of the partial pressures; partial pressure = mole fraction × total pressure
- Graham's law: rate1/rate2 = √(M2/M1)
- K = °C + 273; °F = (9/5 × °C) + 32; 1 atm = 760 torr = 101 325 Pa; 1 cal = 4.18 J
Kinetic theory and real gases
- Postulates: the volume of the molecules is negligible; there are no forces between them; collisions are perfectly elastic; motion is random
- average kinetic energy ∝ absolute temperature (in K), and it is the same for all gases at the same temperature
- root mean square speed = √(3RT/M), so lighter molecules move faster at the same temperature
- Real gases are most ideal at low pressure and high temperature; they deviate most at high pressure and low temperature
- van der Waals equation: (P + n2a/V2)(V − nb) = nRT; a corrects for attractions, b for the volume of the molecules
- PV/nRT < 1: attractions dominate; PV/nRT > 1: the volume of the molecules dominates (very high pressure)
- Plasma examples: the Sun and stars, lightning, neon signs, fluorescent tubes
Chemistry · Liquids
Intermolecular forces
- London forces: the only force between non-polar molecules (Br2, CH4, noble gases); stronger with more electrons and a longer, less branched shape
- Dipole–dipole forces: between polar molecules such as HCl, propanone and ethanal
- Hydrogen bond: H joined to N, O or F is attracted to a lone pair on N, O or F of another molecule
- For molecules of similar size: hydrogen bond > dipole–dipole > London; all are far weaker than a covalent bond
- Hydrogen-bond strength: F–H···F > O–H···O > N–H···N; water still boils higher than HF because each molecule can form more hydrogen bonds
- Ice: each H2O is hydrogen bonded to 4 others in an open tetrahedral structure, so ice is less dense than water; water is densest at 4 °C
- Carboxylic acids form hydrogen-bonded dimers; hydrogen bonds hold the two strands of DNA together
Properties of liquids
- Vapour pressure rises with temperature along a curve; it does not depend on the amount of liquid, the surface area or the size of the container
- Boiling point: the temperature at which vapour pressure = external pressure (100 °C for water at 760 torr); lower pressure gives a lower boiling point
- Stronger intermolecular forces: lower vapour pressure, higher boiling point, larger heat of vaporisation
- Evaporation is faster at a higher temperature, with a larger surface area and with weaker intermolecular forces
- heat for a change of state = moles × molar heat of fusion (or of vaporisation); melting, boiling and sublimation absorb heat; freezing and condensation release it
- Molar heat of vaporisation is larger than molar heat of fusion for the same substance
- Surface tension pulls a drop into a sphere; water rises in a glass capillary (adhesion > cohesion), mercury is pushed down (cohesion > adhesion)
Chemistry · Solids
Crystalline solids
- Unit cell: 6 parameters (edges a, b, c and angles α, β, γ); 7 crystal systems, e.g. cubic a = b = c, α = β = γ = 90°
- Ionic (NaCl): hard, brittle, high melting point, conducts only when molten or dissolved; in NaCl each ion has 6 nearest neighbours of the other kind
- Covalent network (diamond, SiO2): very hard, very high melting point. Molecular (ice, I2, dry ice): soft, low melting point, non-conductor
- Metallic: positive ions in a sea of free electrons; conducts as a solid, malleable and ductile
- Lattice energy is larger for smaller ions and for ions of higher charge
- Isomorphism: different substances, same crystal form (NaF and MgO, both cubic). Polymorphism: one compound, more than one crystal form. Allotropy: the same for an element (diamond and graphite)
- Radius ratio r+/r−: 0.225 to 0.414 gives coordination number 4; 0.414 to 0.732 gives 6; 0.732 to 1.0 gives 8
Chemistry · Chemical equilibrium
Equilibrium and Le Chatelier's principle
- For aA + bB ⇌ cC + dD: Kc = [C]c[D]d ÷ [A]a[B]b; Kp uses partial pressures in the same way; pure solids and liquids are left out
- Kp = Kc(RT)Δn, where Δn = moles of gaseous products − moles of gaseous reactants; Kp = Kc when Δn = 0
- Reaction quotient Q: if Q < K the reaction moves forward; if Q > K it moves backward
- Adding a reactant or removing a product shifts the equilibrium forward; K does not change
- Higher pressure shifts towards the side with fewer moles of gas; higher temperature shifts in the endothermic direction
- A catalyst speeds up both directions equally: equilibrium is reached sooner, with no change in position or in K
- Haber process: N2 + 3H2 ⇌ 2NH3, ΔH = −92 kJ mol−1; high pressure (about 200 atm), about 400 to 450 °C as a compromise, iron catalyst
Ionic equilibria
- Arrhenius: an acid gives H+ in water, a base gives OH−. Brønsted–Lowry: an acid donates a proton, a base accepts one. Lewis: an acid accepts an electron pair, a base donates one
- pH = −log[H+]; pOH = −log[OH−]; pH + pOH = pKw = 14 at 25 °C (Kw = 1.0 × 10−14 mol2 dm−6)
- Ka = [H+][A−] ÷ [HA]; pKa = −log Ka; a larger Ka (smaller pKa) means a stronger acid
- Weak acid of concentration c: [H+] = √(Ka × c)
- Ksp for AxBy = [A]x[B]y; with solubility s: AB gives s2, AB2 or A2B gives 4s3
- A precipitate forms only when the ionic product is greater than Ksp
- Buffer: pH = pKa + log([salt] ÷ [acid]); blood is kept at pH 7.35 to 7.45, mainly by H2CO3 / HCO3−
Chemistry · Reaction kinetics
Rate and rate law
- rate = change in concentration ÷ time taken; unit mol dm−3 s−1
- For aA → bB: rate = −(1/a) × Δ[A]/Δt = (1/b) × Δ[B]/Δt
- Rate law: rate = k[A]x[B]y; overall order = x + y; k is the rate when every concentration is 1 mol dm−3 and changes only with temperature
- Units of k: zero order mol dm−3 s−1; first order s−1; second order dm3 mol−1 s−1
- Half-life: first order t½ = 0.693 ÷ k, constant; zero order t½ ∝ starting concentration; second order t½ ∝ 1 ÷ starting concentration
- After n half-lives of a first-order reaction, the fraction left = (½)n
- Methods: colour (spectrometry), electrical conductivity, optical rotation, volume change (dilatometry), or titration of samples; a reactant in large excess gives a pseudo-first-order reaction
Activation energy and catalysis
- ΔH = Ea(forward) − Ea(reverse). Exothermic: the forward barrier is the smaller one. Endothermic: the forward barrier is the larger one.
- Higher concentration (or gas pressure) and larger surface area: more collisions per second, so a faster rate.
- Higher temperature: a much larger fraction of molecules have energy of at least Ea. The rate roughly doubles for each 10 °C rise.
- Lower Ea means a faster reaction at the same temperature. ΔH does not decide the rate.
- Arrhenius equation: k = Ae−Ea/RT. A graph of ln k against 1/T is a straight line of slope −Ea/R.
- Homogeneous catalyst: same phase as the reactants. Heterogeneous catalyst: different phase. Autocatalysis: a product catalyses the reaction (Mn2+ in the KMnO4 and oxalic acid reaction).
- An inhibitor (negative catalyst) slows a reaction. A catalyst never changes ΔH or the position of equilibrium.
Chemistry · Thermochemistry and energetics
Enthalpy changes
- Formation, ΔH°f: one mole of a compound is formed from its elements in their standard states. For an element in its standard state ΔH°f = 0.
- Combustion, ΔH°c: one mole of a substance burns completely in excess oxygen. It is always negative.
- Atomisation: one mole of gaseous atoms is formed from the element. It is always positive.
- Neutralisation: one mole of water is formed from an acid and a base; about −57 kJ mol−1 for any strong acid with a strong base.
- ΔH = (sum of bond energies of bonds broken) − (sum of bond energies of bonds formed).
- Heat = mass × specific heat capacity × temperature change (q = mcΔT); for a whole calorimeter q = CΔT with C in J K−1. Then ΔH = −q ÷ moles, in kJ mol−1.
- Food energy: fat gives about 38 kJ g−1, carbohydrate and protein about 17 kJ g−1 each.
First law and Hess's law
- ΔE = q + w. q is positive when the system absorbs heat; w is positive when work is done on the system.
- Work of a gas at constant pressure: w = −PΔV. Expansion gives a negative w. 1 kPa × 1 dm3 = 1 J.
- At constant volume no work is done, so qv = ΔE. At constant pressure qp = ΔH, where H = E + PV and ΔH = ΔE + PΔV.
- Hess's law: if an equation is reversed, change the sign of ΔH; if it is multiplied, multiply ΔH by the same number; then add.
- ΔH° = ΣΔH°f(products) − ΣΔH°f(reactants), each multiplied by its coefficient in the equation.
- Born–Haber cycle: ΔH°f = atomisation of the metal + ionisation energy + atomisation of the non-metal + electron affinity + lattice energy.
- Lattice energy is the energy released when one mole of an ionic solid forms from its gaseous ions, so it is negative. Atomisation and ionisation are endothermic.
Chemistry · Electrochemistry
Oxidation numbers and redox
- A free element is 0. A simple ion equals its charge. The numbers add up to 0 in a compound and to the charge in a polyatomic ion.
- Group 1 metals are +1, group 2 metals +2, fluorine always −1. Hydrogen is +1, but −1 in metal hydrides such as NaH.
- Oxygen is −2, except −1 in peroxides (H2O2), −½ in superoxides (KO2) and +2 in OF2.
- Balancing in acid: balance the main atoms, add H2O for oxygen, H+ for hydrogen and electrons for charge; then multiply the half-equations so the electrons cancel.
- An element in its highest state can only be an oxidising agent (Mn in MnO4−); in its lowest state only a reducing agent (I−); in between it can be both (H2O2, SO2).
- Disproportionation: the same element is oxidised and reduced in one reaction.
Electrode potentials and cells
- SHE: hydrogen gas at 1 atm bubbles over platinum coated with platinum black, in 1 M H+ at 298 K. Its E° is 0.00 V by convention.
- Standard conditions: ion concentration 1 M, temperature 298 K, gases at 1 atm.
- E°cell = E°(cathode) − E°(anode), using reduction potentials. A positive value means the reaction is feasible.
- In both kinds of cell, oxidation is at the anode and reduction is at the cathode. Galvanic: anode is negative. Electrolytic: anode is positive.
- A metal with a negative E° displaces hydrogen from dilute acid, and a metal displaces from solution the ions of any metal with a more positive E°.
- The salt bridge (|| in cell notation) lets ions move between the half-cells, keeping the solutions neutral and completing the circuit.
- Lead accumulator: anode Pb, cathode PbO2, electrolyte dilute H2SO4. Electrolysis is used to refine copper, extract aluminium and electroplate.
Chemistry · Chemical bonding
Ionic and covalent bonding
- An ionic bond forms most easily between a metal of low ionisation energy and a non-metal that releases much energy on gaining an electron.
- Coordinate bond: the donor needs a lone pair and the acceptor an empty orbital, as in NH4+, H3O+ and Al2Cl6.
- Electronegativity difference: 0 is non-polar covalent; up to about 1.7 is polar covalent; above 1.7 is mainly ionic.
- Dipole moment = charge × distance between the charges (μ = q × r), unit debye (D). In symmetrical molecules (CO2, BF3, CH4, CCl4) the bond dipoles cancel, so μ = 0.
- Bond energy: the energy needed to break one mole of a bond in gaseous molecules, in kJ mol−1.
- More shared pairs give a shorter, stronger bond: C–C is longer and weaker than C=C, which is longer and weaker than C≡C. Bond length ≈ sum of the two covalent radii.
- Fajans' rules: a small, highly charged cation with a large anion gives more covalent character (AlCl3 > MgCl2 > NaCl).
Shapes of molecules
- Repulsion: lone pair–lone pair > lone pair–bond pair > bond pair–bond pair.
- 2 regions: linear, 180°, sp (BeCl2, CO2). 3 regions: trigonal planar, 120°, sp2 (BF3). 4 regions: tetrahedral, 109.5°, sp3 (CH4).
- 5 bond pairs: trigonal bipyramidal, 90° and 120° (PCl5). 6 bond pairs: octahedral, 90° (SF6).
- Four pairs with lone pairs: NH3 (one lone pair) is trigonal pyramidal, 107.5°; H2O (two lone pairs) is bent, 104.5°.
- s-character: sp 50%, sp2 33%, sp3 25%.
- Single bond = 1σ; double bond = 1σ + 1π; triple bond = 1σ + 2π. A σ bond is stronger because head-on overlap is greater; π electron density lies above and below the line joining the nuclei.
- Molecular orbital theory: O2 has two unpaired electrons in antibonding π orbitals, so it is paramagnetic, with bond order 2.
Chemistry · s and p block elements
Periodic trends and the s block
- Across a period: atomic radius decreases; ionisation energy, electronegativity and the energy released on gaining an electron generally increase. Down a group: the opposite.
- Exceptions: first ionisation energy Al < Mg (3p electron, shielded by 3s) and S < P (paired 3p electron is repelled). Cl releases more energy than F on gaining an electron. Adding a second electron (O− → O2−) absorbs energy.
- Period 3 melting points: rise Na < Mg < Al (more delocalised electrons), highest at Si (giant covalent), then low for the small molecules: S8 > P4 > Cl2 > Ar.
- A positive ion is smaller than its atom and a negative ion is larger. For ions with the same number of electrons, more protons means a smaller ion.
- Burning in excess oxygen: Li gives Li2O, Na gives Na2O2 (peroxide), K gives KO2 (superoxide). Only Li in group 1 forms a nitride, Li3N.
- Down group 2: hydroxides become more soluble and more basic; sulphates become less soluble (BaSO4 least); carbonates, nitrates and hydroxides need stronger heating to decompose. BeO is amphoteric.
- Flame colours: Li crimson, Na golden yellow, K lilac, Ca brick red, Sr crimson, Ba apple green. Be and Mg give no colour.
The p block
- F2 pale yellow gas, Cl2 greenish-yellow gas, Br2 red-brown liquid, I2 grey-black solid. Oxidising power: F2 > Cl2 > Br2 > I2.
- A halogen displaces a less reactive halogen from its halide: Cl2 + 2KBr → 2KCl + Br2.
- Acid strength: HF < HCl < HBr < HI (the H–X bond gets weaker), and HOCl < HClO2 < HClO3 < HClO4 (more oxygen atoms).
- Cold dilute alkali: Cl2 + 2NaOH → NaCl + NaOCl + H2O. Hot concentrated alkali: 3Cl2 + 6NaOH → 5NaCl + NaClO3 + 3H2O.
- Period 3 oxides: Na2O and MgO basic; Al2O3 amphoteric; SiO2, P4O10, SO3 and Cl2O7 acidic. Chlorides: NaCl neutral; AlCl3, SiCl4 and PCl5 are hydrolysed, giving acidic solutions with HCl.
- Concentrated HNO3 turns yellow in light: 4HNO3 → 4NO2 + 2H2O + O2. Concentrated H2SO4 (oil of vitriol) is a dehydrating and oxidising agent. Blue vitriol is CuSO4·5H2O.
- Aluminium: bauxite (Al2O3·2H2O) is purified to alumina, dissolved in molten cryolite (Na3AlF6) to lower the working temperature, and electrolysed.
Chemistry · Transition elements
Properties of transition elements
- General configuration: (n−1)d1–10 ns1–2. Exceptions: Cr is [Ar] 3d5 4s1 and Cu is [Ar] 3d10 4s1, because half-filled and full d subshells are extra stable.
- Zn and Zn2+ both have a full 3d10 subshell, so zinc is not a typical transition element: its ion is colourless and diamagnetic.
- Highest oxidation state from Sc to Mn = number of 4s + 3d electrons: Cr +6, Mn +7.
- More unpaired electrons means stronger paramagnetism: Mn2+ and Fe3+ (3d5) have five. Ions with no unpaired electron (Sc3+, Cu+, Zn2+) are diamagnetic and colourless.
- Catalysts: Fe in the Haber process, V2O5 in the Contact process, Ni for hydrogenation of oils.
- Brass = Cu + Zn; bronze = Cu + Sn. Interstitial compounds (C in Fe) are harder and stronger than the pure metal. Binding energy rises to the middle of the 3d series, then falls to its lowest at Zn.
- 2CrO42− (yellow) + 2H+ ⇌ Cr2O72− (orange) + H2O. Acid gives orange, alkali gives yellow. Cr is +6 in both, so it is not redox.
Complexes
- Monodentate ligands (one donor atom): H2O, NH3, Cl−, CN−, OH−. Bidentate (two): ethylenediamine (en), oxalate C2O42−.
- Coordination number = number of donor atoms bonded to the metal, not the number of ligands: [Co(en)3]3+ has 6.
- Oxidation number of the metal = charge on the complex ion − total charge of the ligands.
- Naming: cation before anion; ligands in alphabetical order with di, tri, tetra, hexa (aqua, ammine, chloro, cyano, hydroxo); then the metal with its oxidation state in Roman numerals. In a complex anion the metal ends in -ate (ferrate, cuprate).
- Shapes: coordination number 2 linear; 4 tetrahedral (sp3) or square planar (dsp2); 6 octahedral (d2sp3 or sp3d2).
- In an octahedral complex the five d orbitals split into three of lower energy and two of higher energy. Ions with d0 or d10 are colourless.
- Stability is greater for a smaller, more highly charged metal ion (Co3+ > Co2+) and for chelating ligands; for 3d ions Mn2+ < Fe2+ < Co2+ < Ni2+ < Cu2+.
Chemistry · Fundamental principles of organic chemistry
Classification and isomerism
- Skeleton: open chain (aliphatic) or cyclic. Cyclic compounds are alicyclic (cyclohexane), aromatic (benzene, naphthalene) or heterocyclic, with N, O or S in the ring (pyridine, furan, thiophene).
- Functional groups: alcohol –OH, aldehyde –CHO, ketone >C=O, carboxylic acid –COOH, ester –COOR, ether R–O–R, amine –NH2, thiol –SH.
- Members of a homologous series differ by CH2. A carbon atom is primary, secondary, tertiary or quaternary when it is bonded to 1, 2, 3 or 4 other carbon atoms.
- Structural isomerism: chain, position, functional group (ethanol and dimethyl ether), metamerism (different alkyl groups on each side of the same group) and tautomerism (shift of an H atom, keto and enol forms).
- Cis-trans isomerism needs a C=C bond (no free rotation) with two different groups on each of its carbon atoms.
- Optical isomerism needs a chiral carbon: one bonded to four different groups. The two mirror-image forms rotate plane-polarised light in opposite directions.
- Fullerene C60: a hollow cage of 20 hexagons and 12 pentagons; each carbon is bonded to three others. It is a molecular form (allotrope) of carbon.
Bonding and reactivity in carbon compounds
- sp3 carbon: 4 σ bonds, tetrahedral, 109.5° (methane, ethane)
- sp2 carbon: 3 σ bonds + 1 π bond, trigonal planar, 120° (ethene, benzene, C=O)
- sp carbon: 2 σ bonds + 2 π bonds, linear, 180° (ethyne, the carbon of C≡N)
- Homolytic fission: A–B → A• + B•. It is favoured by non-polar bonds, ultraviolet light or heat
- Heterolytic fission: A–B → A+ + B−. It is favoured by polar bonds and polar solvents; the more electronegative atom takes both electrons
- Electrophiles are positive or electron-deficient: H+, NO2+, Br+, AlCl3, BF3, SO3
- Nucleophiles have a lone pair to give: OH−, CN−, Cl−, NH3, H2O
Chemistry · Hydrocarbons
Alkanes and alkenes
- Initiation: Cl2 → 2Cl• (light). Propagation: Cl• + CH4 → •CH3 + HCl, then •CH3 + Cl2 → CH3Cl + Cl•. Termination: two radicals join
- Reactivity of halogens with alkanes: F2 > Cl2 > Br2 > I2
- Markovnikov's rule: when HX adds to an unsymmetrical alkene, H goes to the carbon that already has more H atoms, because the more stable carbocation forms
- Reactivity of HX with alkenes: HI > HBr > HCl (the weakest H–X bond breaks most easily)
- Tests for C=C: bromine turns from red-brown to colourless; cold, dilute, alkaline KMnO4 (Baeyer's reagent) loses its purple colour and a diol forms
- Alkenes are made by dehydrating alcohols (concentrated H2SO4 at about 170 °C, or hot Al2O3), by heating alkyl halides with alcoholic KOH, or from vicinal dihalides with zinc dust
- More branching gives a lower boiling point; a cycloalkane boils higher than the straight-chain alkane with the same number of carbon atoms
Alkynes and benzene
- Terminal alkynes give a white precipitate with ammoniacal AgNO3 and a reddish-brown precipitate with ammoniacal Cu2Cl2; they also react with Na or NaNH2
- Hydration of an alkyne (dilute H2SO4, HgSO4): ethyne gives ethanal, all other alkynes give ketones
- Benzene: all C–C bonds 139 pm (between C–C and C=C), bond angle 120°, resonance energy about 150 kJ mol−1
- Nitration: concentrated HNO3 + concentrated H2SO4, electrophile NO2+. Sulphonation: fuming H2SO4, electrophile SO3
- Halogenation: Cl2 or Br2 with FeCl3, FeBr3 or AlCl3. Friedel–Crafts: RCl or RCOCl with anhydrous AlCl3 (a Lewis acid that makes R+ or RCO+)
- –CH3 and –OH activate the ring and direct to positions 2 and 4; –NO2 deactivates the ring and directs to position 3
- Faraday discovered benzene in 1825; Kekulé proposed the ring structure in 1865. Toluene = methylbenzene, cumene = (1-methylethyl)benzene
Chemistry · Alkyl halides
Alkyl halides
- Reactivity: R–I > R–Br > R–Cl > R–F (C–F is the strongest bond)
- SN2: one step, rate = k[RX][Nu−], attack from the back, inversion of configuration. Order: primary > secondary > tertiary
- SN1: two steps, slow step forms a carbocation, rate = k[RX], product is mostly racemic. Order: tertiary > secondary > primary
- E2: one step, rate depends on both halide and base. E1: two steps through a carbocation, rate depends on the halide only
- Aqueous KOH favours substitution (alcohol); hot concentrated alcoholic KOH favours elimination (alkene). Tertiary halides eliminate most easily
- R–X + Mg in dry ether → R–Mg–X (Grignard reagent); with water it gives the alkane R–H. Wurtz: 2R–X + 2Na → R–R + 2NaX
- Boiling points: R–I > R–Br > R–Cl for the same R, and branching lowers them. Freons (CFCs) were refrigerants and aerosol propellants; their Cl atoms destroy ozone
Chemistry · Alcohols and phenols
Alcohols
- Oxidation with acidified K2Cr2O7 (orange to green): primary → aldehyde → carboxylic acid; secondary → ketone; tertiary → no oxidation
- Lucas reagent (concentrated HCl + anhydrous ZnCl2): tertiary turns cloudy at once, secondary in 5 to 10 minutes, primary stays clear at room temperature
- Concentrated H2SO4: about 170 °C with excess acid gives an alkene; about 140 °C with excess alcohol gives an ether
- Esterification: RCOOH + R′OH ⇌ RCOOR′ + H2O (concentrated H2SO4). The acid loses –OH and the alcohol loses H
- 2ROH + 2Na → 2RONa + H2. ROH + SOCl2 → RCl + SO2 + HCl. ROH + PCl5 → RCl + POCl3 + HCl
- Iodoform test (I2 + NaOH, yellow precipitate of CHI3): positive for CH3CH(OH)–, so ethanol and propan-2-ol react but methanol does not
- Made by: hydration of alkenes, hydrolysis of alkyl halides with aqueous NaOH, Grignard reagent + carbonyl compound, reduction of aldehydes, ketones and acids, fermentation (ethanol)
Phenols and ethers
- Acid strength: carboxylic acid > phenol > water > alcohol. Ka of phenol is about 1 × 10−10
- Phenol reacts with NaOH to give sodium phenoxide and water, but it gives no CO2 with Na2CO3 or NaHCO3
- Electron-withdrawing groups (–NO2) make a phenol more acidic; electron-donating groups (–CH3) make it less acidic
- Bromine water at room temperature: white precipitate of 2,4,6-tribromophenol. Dilute HNO3: 2- and 4-nitrophenol. Concentrated HNO3 + H2SO4: 2,4,6-trinitrophenol (picric acid)
- Phenol + zinc dust (heat) → benzene + ZnO. Phenol + methanal → Bakelite. Phenol + CH3COCl → phenyl ethanoate + HCl
- Phenol (carbolic acid): colourless crystals, melting point 41 °C, absorbs moisture from air, turns pink in air by oxidation. Catechol, resorcinol and quinol are benzene-1,2-, 1,3- and 1,4-diol
- Ethers are named alkoxyalkanes, with the smaller group as alkoxy: CH3OC2H5 is methoxyethane. Oxygen is sp3, so C–O–C is bent, about 110°. Williamson: RONa + R′X → ROR′ + NaX
Chemistry · Aldehydes and ketones
Aldehydes and ketones
- General formula CnH2nO. An aldehyde and a ketone with the same formula are functional group isomers (propanal and propanone)
- 2,4-DNPH: yellow or orange precipitate with both aldehydes and ketones (test for C=O)
- Tollens' reagent: silver mirror with aldehydes only. Fehling's solution: brick-red Cu2O with aliphatic aldehydes only (not benzaldehyde, not ketones)
- Iodoform test (I2 + NaOH, yellow CHI3): positive for CH3CO–, so ethanal and methyl ketones. Alkaline sodium nitroprusside: red colour with ketones
- HCN (with a little NaCN) adds to give a hydroxynitrile (cyanohydrin); the attacking species is CN−. Saturated NaHSO3 gives white crystals with aldehydes and small methyl ketones
- Reduction (NaBH4, LiAlH4 or H2/Ni): aldehyde → primary alcohol, ketone → secondary alcohol. Zn/Hg + concentrated HCl (Clemmensen) changes C=O to CH2
- Dilute NaOH: aldol condensation if there is an α-hydrogen. Concentrated NaOH: Cannizzaro reaction if there is no α-hydrogen (methanal, benzaldehyde)
Chemistry · Carboxylic acids
Carboxylic acids and derivatives
- Acid strength: ClCH2COOH > HCOOH > C6H5COOH > CH3COOH > CH3CH2COOH. A larger Ka (smaller pKa) means a stronger acid
- Made by: oxidising primary alcohols or aldehydes; hydrolysing nitriles (RCN → RCOOH); Grignard reagent + CO2, then dilute acid; oxidising the side chain of an alkylbenzene to benzoic acid
- Acids react with metals, alkalis and carbonates; CO2 from Na2CO3 or NaHCO3 is the test for –COOH
- RCOOH + PCl5 → RCOCl + POCl3 + HCl. RCOOH + SOCl2 → RCOCl + SO2 + HCl. 3RCOOH + PCl3 → 3RCOCl + H3PO3
- Reactivity towards nucleophiles: acid chloride > anhydride > ester > amide
- Ester hydrolysis: with dilute acid it is reversible; with NaOH it goes to completion, giving the sodium salt of the acid and the alcohol
- LiAlH4 reduces RCOOH to RCH2OH. Decarboxylation: RCOONa + NaOH (soda lime, heat) → RH + Na2CO3
Chemistry · Macromolecules
Polymers
- Addition polymers: polyethene from CH2=CH2; PVC from CH2=CHCl; polystyrene from C6H5CH=CH2; Teflon (PTFE) from CF2=CF2; polyacrylonitrile from CH2=CHCN
- To find the monomer of an addition polymer, take the two-carbon repeating unit and put the double bond back between the two chain carbons
- Nylon-6,6 (a polyamide): hexanedioic acid + hexane-1,6-diamine, joined by amide links –CO–NH–, water lost
- Terylene or Dacron (a polyester): benzene-1,4-dicarboxylic acid + ethane-1,2-diol, joined by ester links –CO–O–, water lost
- Bakelite: phenol + methanal, a condensation polymer with cross-links between chains
- Thermoplastics (polyethene, PVC, nylon) soften on heating and can be remoulded; thermosetting plastics (Bakelite) are cross-linked and cannot be remoulded
- Number of monomer units in an addition polymer chain = Mr of polymer ÷ Mr of monomer
Biological macromolecules
- Fibrous proteins are insoluble and structural (collagen, keratin). Globular proteins are folded and soluble (enzymes, haemoglobin, insulin, albumin)
- Simple proteins give only amino acids on hydrolysis; conjugated proteins also have a non-protein part (haemoglobin has haem)
- Primary structure = sequence of amino acids, held by peptide bonds. The α-helix is held by hydrogen bonds between C=O and N–H groups
- Competitive inhibitor: looks like the substrate, blocks the active site, overcome by adding more substrate. Non-competitive inhibitor: binds elsewhere, not overcome by more substrate
- Cofactors: metal ions or organic coenzymes such as NAD+. A zymogen is an inactive form of an enzyme (pepsinogen, trypsinogen) that becomes active when part of its chain is cut off
- Reducing sugars (glucose, fructose, maltose, lactose) reduce Fehling's solution; sucrose does not. Starch and cellulose are polymers of glucose
- Iodine number = grams of iodine taken up by 100 g of fat; a high value means many C=C bonds. A nucleotide = pentose sugar + phosphate group + nitrogenous base
Chemistry · Industrial chemistry
Industrial chemistry
- Urea: 2NH3 + CO2 → NH2COONH4 (ammonium carbamate), then NH2COONH4 → CO(NH2)2 + H2O. Urea is about 46 to 47% nitrogen by mass (28 ÷ 60)
- Ammonium nitrate: NH3 + HNO3 → NH4NO3
- Single superphosphate: Ca3(PO4)2 + 2H2SO4 → Ca(H2PO4)2 + 2CaSO4
- Triple superphosphate: Ca3(PO4)2 + 4H3PO4 → 3Ca(H2PO4)2 (no CaSO4, so more phosphorus per kg)
- Cracking: a large alkane → a smaller alkane + an alkene, for example C10H22 → C8H18 + C2H4
- Octane number: 2,2,4-trimethylpentane (iso-octane) = 100, heptane = 0. Reforming changes straight chains into branched, ring and aromatic molecules to raise it
- Ethene from cracking gives polyethene, ethanol and ethane-1,2-diol
Physics · Vectors and equilibrium
Vectors and components
- Components of A at angle θ to the positive x-axis: Ax = A cos θ, Ay = A sin θ
- Adding by components: Rx = Ax + Bx + ..., Ry = Ay + By + ...
- magnitude of resultant: R = √(Rx2 + Ry2)
- direction of resultant: tan θ = Ry/Rx, then pick the quadrant from the signs of Rx and Ry
- Two vectors A and B with angle θ between them: R = √(A2 + B2 + 2AB cos θ)
- Greatest resultant = A + B (same direction); least resultant = A − B (opposite directions)
- Weight mg on a slope at angle θ to the horizontal: mg sin θ down the slope, mg cos θ into the slope
Products of vectors and torque
- scalar product: A · B = AB cos θ = AxBx + AyBy + AzBz; A · A = A2
- vector product: size of A × B = AB sin θ, direction perpendicular to the plane of A and B (right-hand rule); B × A = −(A × B)
- Unit vectors: i · i = 1, i · j = 0, i × i = 0, i × j = k
- tan θ = (size of A × B) ÷ (A · B)
- torque = force × perpendicular distance from the pivot (τ = rF sin θ), unit N m
- torque of a couple = one force × perpendicular distance between the two forces
- Equilibrium: first condition ΣF = 0; second condition Στ = 0 (clockwise torques = anticlockwise torques)
Physics · Force and motion
Kinematics
- average velocity = total displacement ÷ total time; average speed = total distance ÷ total time
- v = u + at
- s = ut + ½at2 and s = ½(u + v)t
- v2 − u2 = 2as
- From rest with uniform acceleration, distances in the 1st, 2nd, 3rd, 4th seconds are in the ratio 1 : 3 : 5 : 7
- Displacement–time graph: slope = velocity. Velocity–time graph: slope = acceleration, area = displacement
- Area below the time axis counts as negative for displacement but is added for distance
Newton's laws and momentum
- First law: no net force means no change in velocity; inertia depends on mass only
- Second law: net force = mass × acceleration (F = ma) = rate of change of momentum (F = Δp/Δt)
- Third law: action and reaction are equal, opposite and act on different bodies, so they never cancel
- momentum = mass × velocity (p = mv), unit kg m s−1 or N s
- impulse = force × time = change in momentum = area under a force–time graph
- Conservation of momentum: m1u1 + m2u2 = m1v1 + m2v2 for an isolated system
- Elastic collision: kinetic energy also conserved, speed of approach = speed of separation. Inelastic collision: some kinetic energy is lost
Projectile motion
- Horizontal: velocity = v cos θ (constant), distance = v cos θ × t
- Vertical: starting velocity = v sin θ, acceleration = g downwards
- time of flight: T = 2v sin θ ÷ g
- maximum height: H = v2 sin2 θ ÷ 2g
- range on level ground: R = v2 sin 2θ ÷ g; greatest at θ = 45°, where Rmax = v2/g
- At the top: vertical velocity = 0, speed = v cos θ, acceleration = g, and velocity is at 90° to acceleration
- Air resistance reduces the range and the maximum height
Physics · Work, power and energy
Work and power
- work = force × displacement × cos θ (W = Fd cos θ), unit joule (J) = N m
- θ = 90°: work is zero. θ greater than 90°: work is negative
- Variable force: work = area under the force–displacement graph
- Spring: work to stretch from 0 to x = ½kx2; from x1 to x2 = ½k(x22 − x12)
- power = work ÷ time = force × velocity (P = W/t = Fv), unit watt (W) = J s−1
- 1 horsepower = 746 W; 1 kW h = 3.6 × 106 J
- efficiency = useful output ÷ total input × 100%
Energy and its conservation
- kinetic energy = ½ × mass × speed2 (KE = ½mv2 = p2/2m)
- gravitational potential energy = mgh, with h measured from the chosen reference level
- Work–energy principle: net work = change in KE (Fd = ½mv2 − ½mu2)
- No friction: loss of PE = gain in KE, so from rest v = √(2gh)
- With friction: loss of PE = gain in KE + work done against friction (f × distance moved)
- elastic potential energy of a spring = ½kx2
Physics · Circular and rotational motion
Angular motion and centripetal force
- angle in radians = arc length ÷ radius (θ = s/r); 2π rad = 360° = 1 revolution
- angular velocity ω = Δθ/Δt in rad s−1; ω = 2π/T = 2πf
- angular acceleration α = Δω/Δt in rad s−2
- Linear and angular: s = rθ, v = rω, a = rα
- ωf = ωi + αt; θ = ωit + ½αt2; θ = ½(ωi + ωf)t; ωf2 − ωi2 = 2αθ
- centripetal acceleration = v2/r = rω2, directed towards the centre
- centripetal force = mv2/r = mrω2
Rotational dynamics
- moment of inertia I = Σmr2, unit kg m2; torque = Iα
- Ring or hoop: I = MR2. Disc or solid cylinder: I = ½MR2. Solid sphere: I = (2/5)MR2. Thin rod about its centre: I = (1/12)ML2
- rotational kinetic energy = ½Iω2
- Rolling without slipping: total KE = ½mv2 + ½Iω2 (disc: ¾mv2; hoop: mv2)
- angular momentum L = Iω = mvr, unit kg m2 s−1 (J s), directed along the axis by the right-hand rule
- Conservation of angular momentum: I1ω1 = I2ω2 when no external torque acts
- Satellite: orbital speed v = √(GM/r); close to the surface v = √(gR), about 7.9 km s−1 for the Earth; T2 ∝ r3
Physics · Fluid dynamics
Viscosity and drag
- Viscosity η measures the internal friction of a fluid; unit N s m−2 (Pa s)
- Stokes' law: drag force = 6πηrv for a small sphere of radius r moving at speed v
- Terminal velocity: drag = weight, net force = 0, acceleration = 0, speed constant
- terminal velocity vt = 2gr2ρ/9η, where ρ is the density of the sphere
- vt ∝ r2 and vt ∝ 1/η: larger drops fall faster, thicker fluids slow the fall
- Laminar flow: steady, in layers, streamlines never cross; streamlines close together mean higher speed
- Turbulent flow: irregular and noisy, begins when the speed passes a critical value
Continuity and Bernoulli
- Continuity: area × speed is constant (A1v1 = A2v2)
- volume flow rate = Av, in m3 s−1
- Bernoulli: P + ½ρv2 + ρgh = constant
- Horizontal pipe: P1 − P2 = ½ρ(v22 − v12), so higher speed means lower pressure
- Torricelli's theorem: speed of efflux from a hole at depth h below the surface is v = √(2gh)
- force from a pressure difference = pressure difference × area
- Conversions: 1 cm2 = 10−4 m2; 1 litre = 10−3 m3
Physics · Waves and oscillations
Simple harmonic motion
- Condition for SHM: a = −ω2x, with ω = 2πf = 2π/T
- displacement: x = x0 sin ωt, where x0 is the amplitude
- speed: v = ω√(x02 − x2); greatest speed = ωx0 at the mean position
- greatest acceleration = ω2x0 at the extreme positions
- Energy: PE = ½kx2, KE = ½k(x02 − x2), total = ½kx02
- Mass–spring system: T = 2π√(m/k), does not depend on g or on the amplitude
- Simple pendulum: T = 2π√(l/g), does not depend on the mass or on a small amplitude
Progressive waves
- wave speed = frequency × wavelength (v = fλ), and f = 1/T
- Phase difference = 2π × distance apart ÷ wavelength (Δφ = 2πx/λ), in radians
- Speed of a transverse wave on a string: v = √(T/μ), with tension T in N and mass per unit length μ in kg m−1
- Coherent sources have the same frequency and a constant phase difference
- Sources in phase: maximum where path difference = nλ, minimum where path difference = (n + ½)λ
- Intensity is proportional to amplitude2, so Imax/Imin = (A1 + A2)2/(A1 − A2)2
- A compression and the nearest rarefaction are half a wavelength apart
Stationary waves and sound
- String fixed at both ends, or pipe open at both ends: fn = nv/(2L), n = 1, 2, 3, …
- Pipe closed at one end: fn = nv/(4L), n = 1, 3, 5, … only
- String vibrating in n loops: L = nλ/2; its fundamental is f1 = (1/(2L)) × √(T/μ)
- Speed of sound in a gas: v = √(γP/ρ) = √(γRT/M), so v is proportional to √T (T in kelvin) and to 1/√M
- Beat frequency = difference of the two frequencies (f1 − f2)
- Doppler, moving source: f′ = f × v/(v − vs) when approaching, f × v/(v + vs) when moving away
- Doppler, moving listener: f′ = f × (v + vo)/v when approaching, f × (v − vo)/v when moving away
Physics · Thermodynamics
Kinetic theory and the first law
- Ideal gas: PV = nRT, and P = ⅓ρ⟨v2⟩ = ⅔ × (N/V) × ⟨½mv2⟩
- Average translational kinetic energy of a molecule = (3/2)kT, with T in kelvin; vrms = √(3RT/M), proportional to √T
- First law: Q = ΔU + W (Q = heat supplied to the gas, W = work done by the gas)
- Isothermal: ΔU = 0, so Q = W
- Adiabatic: Q = 0, so W = −ΔU (compression heats the gas, expansion cools it)
- Isochoric: W = 0, so Q = ΔU
- Isobaric: W = PΔV = nRΔT
Heat engines and entropy
- efficiency = work output ÷ heat input: η = W/Q1 = 1 − Q2/Q1
- Carnot engine: η = 1 − T2/T1, and Q2/Q1 = T2/T1 (T1 source, T2 sink, both in kelvin)
- A real engine is always less efficient than a Carnot engine between the same temperatures; 100% would need a sink at 0 K
- Entropy change ΔS = Q/T, unit J K−1; positive for heat gained, negative for heat lost
- Total entropy increases in an irreversible process and stays constant in a reversible one; it never decreases
- Melting and boiling raise the entropy of a substance; freezing and condensing lower it
Physics · Electrostatics
Coulomb's law and electric field
- Coulomb's law in a vacuum: F = kq1q2/r2, with k = 1/(4πε0) = 9 × 109 N m2 C−2
- In a medium: Fmedium = Fvacuum ÷ εr, so εr = Fvacuum/Fmedium
- electric field strength = force ÷ charge (E = F/q), unit N C−1 or V m−1
- Field of a point charge: E = kq/r2
- Uniform field between parallel plates: E = V/d
- Field lines start on positive charges and end on negative charges, never cross, and are closer together where the field is stronger
Potential and capacitors
- potential difference = work done ÷ charge (V = W/q); energy gained by a charge = qV
- Point charge: V = kq/r; field strength is the potential gradient, E = −ΔV/Δr, so for a point charge E = V/r
- 1 eV = 1.6 × 10−19 J
- capacitance = charge ÷ potential difference (C = Q/V); 1 F = 1 C V−1
- Parallel-plate capacitor: C = ε0εrA/d
- Parallel: C = C1 + C2 + …; series: 1/C = 1/C1 + 1/C2 + …
- Energy stored = ½QV = ½CV2 = Q2/(2C)
Physics · Current electricity
Resistance and Ohm's law
- current = charge ÷ time (I = Q/t), and Q = ne with e = 1.6 × 10−19 C
- Ohm's law: V = IR, with R constant at constant temperature
- resistance = resistivity × length ÷ area (R = ρL/A); ρ in Ω m; A = πd2/4
- Temperature: Rt = R0(1 + αΔt); α is positive for metals
- Series: R = R1 + R2 + …
- Parallel: 1/R = 1/R1 + 1/R2 + …; for two resistors R = R1R2/(R1 + R2)
- n equal resistors R in parallel give R/n
Circuits, EMF and power
- Terminal p.d. = EMF − lost volts: V = E − Ir
- Current from a cell: I = E/(R + r)
- power = p.d. × current: P = VI = I2R = V2/R
- energy = power × time; 1 kW h = 3.6 × 106 J
- Kirchhoff's first rule: total current into a junction = total current out
- Kirchhoff's second rule: round any closed loop, sum of EMFs = sum of IR drops; EMFs that oppose are subtracted
- Balanced Wheatstone bridge: P/Q = R/S
Physics · Electromagnetism
Magnetic fields and forces
- Long straight wire: B = μ0I/(2πr), with μ0 = 4π × 10−7 T m A−1
- Inside a solenoid: B = μ0nI, where n = N/L is the number of turns per metre
- force on a wire = B × I × L × sin θ (F = BIL sin θ), θ between the wire and the field
- Direction of the force: Fleming's left-hand rule (first finger field, second finger current, thumb force)
- Parallel wires: force per unit length F/L = μ0I1I2/(2πd), the same size on both wires
- Fields from two wires add as vectors: between wires with opposite currents they add; between wires with the same currents they subtract
- 1 T = 1 N A−1 m−1
Charges in magnetic fields
- force on a moving charge = q × v × B × sin θ (F = qvB sin θ), θ between velocity and field
- Circular path: qvB = mv2/r, so r = mv/(qB) = √(2mEk)/(qB)
- Period T = 2πm/(qB), which does not depend on the speed or the radius
- Electrons accelerated through V: eV = ½mv2, which gives e/m = 2V/(B2r2)
- Direction: Fleming's left-hand rule for a positive charge; reverse it for an electron
- Ammeter: shunt in parallel, Rs = IgRg/(I − Ig)
- Voltmeter: series resistance Rh = V/Ig − Rg
Physics · Electromagnetic induction
Faraday's and Lenz's laws
- magnetic flux = B × A × cos θ (Φ = BA cos θ), θ between the field and the normal to the loop; unit weber, 1 Wb = 1 T m2
- Faraday's law: EMF = −N × ΔΦ/Δt
- Motional EMF of a rod cutting the field at right angles: EMF = BLv; induced current I = BLv/R
- Lenz's law: the induced current opposes the change in flux that produces it (the minus sign in Faraday's law)
- A north pole approaching a coil makes the near face a north pole (repels); a north pole moving away makes it a south pole (attracts)
- Seen from outside, a face with anticlockwise current is a north pole and a face with clockwise current is a south pole
Inductance, generators and transformers
- Self-induced EMF = −L × ΔI/Δt; L in henry, 1 H = 1 V s A−1
- Mutual induction: EMF in secondary = −M × ΔIp/Δt
- Energy stored in an inductor = ½LI2
- Generator: EMF = NBAω sin θ, θ between the field and the normal to the coil; peak EMF E0 = NBAω, with ω = 2πf
- Transformer turns ratio: Vs/Vp = Ns/Np
- Ideal transformer: VpIp = VsIs, so Is/Ip = Np/Ns
- Laminated core reduces eddy currents; soft iron reduces hysteresis loss
Physics · Alternating current
AC quantities
- V = V0 sin ωt, with ω = 2πf and T = 1/f
- rms value = peak value ÷ √2 (Vrms = V0/√2 = 0.707 V0; Irms = I0/√2)
- peak-to-peak value = 2 × peak value
- average power = rms voltage × rms current × power factor (P = Vrms Irms cos φ)
- For a resistor: P = Irms2R = Vrms2/R = V02/2R
- A sine wave goes from zero to its peak in a quarter of a period (T/4)
- Mains values such as 220 V are rms values
AC circuits
- inductive reactance = 2π × frequency × inductance (XL = ωL = 2πfL), in Ω
- capacitive reactance = 1 ÷ (2π × frequency × capacitance) (XC = 1/ωC = 1/(2πfC)), in Ω
- impedance of a series RLC circuit: Z = √(R2 + (XL − XC)2), and Irms = Vrms/Z
- supply voltage in a series circuit: V = √(VR2 + (VL − VC)2)
- phase angle: tan φ = (XL − XC)/R; current lags if XL > XC, leads if XC > XL
- resonant frequency: f0 = 1/(2π√(LC))
- At series resonance: Z = R, current is maximum and in phase with the supply voltage
Physics · Physics of solids and electronics
Properties of solids
- stress = force ÷ area (σ = F/A), in Pa or N m−2
- strain = extension ÷ original length (ε = ΔL/L), no unit
- Young's modulus = stress ÷ strain (Y = FL/(AΔL)), in Pa
- Order on the stress-strain curve: proportional limit, elastic limit, yield point, ultimate tensile strength (highest stress), breaking point
- elastic energy stored = ½ × force × extension (within the proportional limit)
- Pentavalent impurity (e.g. arsenic) gives n-type: electrons are majority carriers. Trivalent impurity (e.g. gallium) gives p-type: holes are majority carriers
- A pure semiconductor at 0 K is an insulator; any doped piece is electrically neutral as a whole
Electronics
- Potential barrier: about 0.7 V for silicon, 0.3 V for germanium. Forward current = (supply voltage − barrier) ÷ series resistance
- Half-wave rectifier: one diode, uses half of each cycle. Full-wave bridge: four diodes, two conduct in each half cycle
- emitter current = base current + collector current (IE = IB + IC)
- current gain = collector current ÷ base current (β = IC/IB)
- Amplifier biasing: base-emitter junction forward biased, collector-base junction reverse biased
- AND: output 1 only if all inputs are 1. OR: output 1 if any input is 1. NOT: output is the opposite of the input
- NAND = AND followed by NOT; NOR = OR followed by NOT; XOR gives 1 when the two inputs are different; XNOR gives 1 when they are the same
Physics · Dawn of modern physics
Photons and the photoelectric effect
- photon energy = Planck's constant × frequency (E = hf = hc/λ), h = 6.6 × 10−34 J s
- Einstein's equation: hf = φ + KEmax, with work function φ = hf0 = hc/λ0
- stopping potential: eV0 = KEmax; 1 eV = 1.6 × 10−19 J
- Graph of KEmax against f: straight line, slope h, intercept on the frequency axis f0
- Compton shift: Δλ = (h/m0c)(1 − cos θ); zero at θ = 0°, greatest at θ = 180°
- Pair production needs a photon of at least 1.02 MeV (2 × 0.51 MeV); any extra becomes kinetic energy of the pair
- Annihilation of an electron and a positron at rest gives two 0.51 MeV photons moving in opposite directions
Wave nature of particles
- de Broglie wavelength = Planck's constant ÷ momentum (λ = h/p = h/mv)
- In terms of kinetic energy: λ = h/√(2mEk); for a charge q accelerated through V, λ = h/√(2mqV)
- Uncertainty principle: Δx Δp ≈ h and ΔE Δt ≈ h
- Time dilation: t = t0/√(1 − v2/c2) (longer)
- Length contraction: L = L0√(1 − v2/c2) (shorter, only along the motion)
- Relativistic mass: m = m0/√(1 − v2/c2)
- Mass-energy: E = mc2, so energy released = mass lost × c2
Physics · Atomic spectra
Bohr model and spectra
- angular momentum: mvr = nh/2π, with n = 1, 2, 3, ...
- radius: rn = n2r1, with r1 = 0.053 nm
- energy: En = −13.6/n2 eV (−13.6, −3.40, −1.51, −0.85 eV for n = 1 to 4); ionisation energy from level n = 13.6/n2 eV
- photon energy: hf = En − Ep
- 1/λ = RH(1/p2 − 1/n2), with RH = 1.1 × 107 m−1
- Series by lower level p: Lyman 1 (ultraviolet), Balmer 2 (visible), Paschen 3, Brackett 4, Pfund 5 (all infrared)
- Number of possible lines from level n down to the ground state = n(n − 1)/2
X-rays and lasers
- maximum photon energy = electron charge × tube voltage (eV = hfmax = hc/λmin), so λmin = hc/eV
- Higher tube voltage: shorter λmin, more penetrating X-rays. Larger filament current: more electrons, greater intensity only
- Kα line: an electron drops from the L shell into a vacancy in the K shell; Kβ: from the M shell
- Dense materials of high atomic number (bone, lead) absorb X-rays more than soft tissue. Uses: radiography, CT scans, cancer therapy, studying crystals
- Metastable state lasts about 10−3 s; an ordinary excited state about 10−8 s
- Laser light is monochromatic, coherent, intense and in a narrow beam
- Helium-neon laser: excited helium atoms pass energy to neon atoms by collision; neon emits red light of 632.8 nm
Physics · Nuclear physics
Nucleus and radioactivity
- mass defect: Δm = Zmp + Nmn − mnucleus
- binding energy = Δm × c2; 1 u = 931 MeV; binding energy per nucleon = binding energy ÷ A
- α decay: A falls by 4, Z falls by 2. β− decay: A unchanged, Z rises by 1. γ emission: A and Z unchanged
- decay law: N = N0e−λt; activity A = λN, in becquerel (1 Bq = 1 decay per second)
- half-life: T½ = 0.693/λ
- After n half-lives: fraction left = (½)n, fraction decayed = 1 − (½)n
Nuclear energy and radiation
- In every nuclear equation the mass numbers and the charge numbers balance on both sides
- energy released = mass lost × c2; 1 u = 931 MeV
- Moderator (graphite, heavy water) slows fast neutrons; control rods (cadmium, boron) absorb neutrons; coolant carries heat out of the core
- Fast breeder reactor: uranium-238 absorbs a neutron and becomes fissile plutonium-239
- Detectors: Geiger-Müller counter (one particle starts an avalanche, giving one pulse), Wilson cloud chamber (tracks of droplets), solid-state detector (reverse-biased p-n junction)
- Units: activity in becquerel (Bq); absorbed dose in gray (1 Gy = 1 J kg−1); equivalent dose in sievert = dose in Gy × RBE
- Somatic effects harm the exposed person; genetic effects appear in their children. Iodine-131 is used for the thyroid, cobalt-60 γ-rays for cancer treatment