⚛ Atoms & Molecules — Complete UPSC Notes
Laws of Chemical Combination · Dalton's Atomic Theory · Molecules, Ions & Valency · Atomic Models (Thomson / Rutherford / Bohr) · Isotopes & Isobars · Mole Concept · PYQs & MCQs
Example: If you burn 12 g of carbon in 32 g of oxygen → you always get exactly 44 g of carbon dioxide. Nothing is lost — atoms are merely rearranged.
Discoverer: Antoine Lavoisier (French chemist, "father of modern chemistry")
UPSC relevance: Basis of Dalton's atomic theory. Also the foundation of stoichiometry (balancing chemical equations).
Example: Water always has hydrogen : oxygen = 1:8 by mass. Whether water comes from rain, a river, or a lab — 9 g of water always gives 1 g H + 8 g O. You can't make water with a different H:O ratio.
Also called: Law of Definite Proportions
Discoverer: Joseph Proust (French chemist, 1799)
- All matter is made of very tiny particles called atoms
- Atoms are indivisible — cannot be created or destroyed in a chemical reaction
- All atoms of a given element are identical in mass and chemical properties
- Atoms of different elements have different masses and properties
- Atoms combine in small whole number ratios to form compounds
- The relative number and kinds of atoms are constant in a given compound
Dalton's Atomic Model — a solid, indivisible sphere with no internal structure. Successfully explained the two laws of chemical combination. Failed when sub-atomic particles (electron by Thomson, proton by Goldstein, neutron by Chadwick) were discovered. Element symbols: proposed by Dalton (pictures), improved by Berzelius (letters), standardised by IUPAC. Some symbols come from Latin names: Fe (Ferrum=Iron), Au (Aurum=Gold), Na (Natrium=Sodium), Cu (Cuprum=Copper), Ag (Argentum=Silver).
• Explains Law of Definite Proportions (fixed atom ratios → fixed mass ratios)
• Introduced atomic mass concept
• Introduced element symbols (Berzelius improved; IUPAC standardised)
• Foundation for all modern chemistry
• Atoms of same element can have different masses (isotopes)
• Atoms of different elements can have same mass (isobars)
• Does not explain allotropes (diamond vs graphite — both carbon)
• Does not explain compounds formed with non-integer ratios (Berthollet found this)
| Particle | Discoverer | Charge | Mass | Location | Symbol |
|---|---|---|---|---|---|
| Electron | J.J. Thomson (1897) Nobel Physics 1906 | −1 (negative) | ~1/2000 of proton; negligible | Orbits / shells around nucleus | e⁻ |
| Proton | Goldstein (1886, canal rays) | +1 (positive) | ~1 u (atomic mass unit) | Inside nucleus | p⁺ |
| Neutron | James Chadwick (1932) Nobel Physics 1935 | 0 (neutral) | ~1 u (≈ proton mass) | Inside nucleus | n° |
Carbon-12 Atom Structure. Nucleus (red) contains 6 protons (p⁺, red) + 6 neutrons (n°, grey). K-shell (inner, orange electrons): 2 electrons. L-shell (outer, green electrons): 4 electrons. Shell capacity formula: 2n² (K=2, L=8, M=18, N=32). Outermost shell maximum: 8 electrons. Atomic number Z = number of protons = 6. Mass number A = p + n = 12. Neutrons = A − Z = 12 − 6 = 6. Valency of Carbon = 4 (needs 4 more electrons to complete octet).
H: Z=1, He: Z=2, Li: Z=3, C: Z=6, N: Z=7, O: Z=8, Na: Z=11, Mg: Z=12, Al: Z=13, Cl: Z=17, Ca: Z=20.
Notation: ᴬ꜀Z X where X = element symbol, A = mass number, Z = atomic number.
Carbon-12: ¹²C₆ → 6p + 6n. Carbon-14: ¹⁴C₆ → 6p + 8n. Both are carbon!
H: 1, He: 0, Li: 1, C: 4, N: 3, O: 2, F: 1, Na: 1, Mg: 2, Al: 3, Cl: 1, Ca: 2
Rule: If outer electrons >4, valency = 8 − outer electrons (gains). If <4, valency = outer electrons (loses).
Three Atomic Models — Evolution. Thomson (1904): Positive charge spread throughout sphere, electrons embedded like plum in pudding (watermelon analogy). ❌ Disproved by Rutherford's gold foil experiment. Rutherford (1911): Tiny dense positive nucleus at centre, electrons orbiting it. ❌ Electrons should spiral into nucleus (Maxwell's laws — accelerating charges radiate energy). Bohr (1913): Electrons in specific fixed orbits (shells K, L, M, N) with discrete energies — they don't radiate energy while in these fixed orbits. ✅ Solved Rutherford's stability problem. All three scientists received Nobel Prizes.
Discovered electron (1897) via cathode ray experiments.
Model: Positive charge uniformly spread like watermelon flesh. Electrons (negative) embedded like seeds in watermelon / plums in pudding. Atom overall neutral.
Success: Explained electrical neutrality.
Failure: Rutherford's experiment showed positive charge concentrated, not spread.
Experiment: α-particles (doubly charged He ions) fired at thin gold foil (~1000 atoms thick).
Observations:
• Most passed straight through → atom mostly empty space
• Some deflected at small angles → small positive charge region
• 1 in 12,000 bounced back → tiny dense positive nucleus
Failure: Accelerating electrons should radiate energy → spiral into nucleus → atom should collapse. Rutherford's atom is unstable!
Postulates:
• Electrons travel only in specific fixed orbits (shells) — K, L, M, N (or n=1,2,3,4)
• While in these orbits, electrons do NOT radiate energy
• Energy is emitted/absorbed only when electrons jump between orbits
• Shell capacity: 2n² (K=2, L=8, M=18, N=32)
• Outermost shell max = 8 electrons
Solved: Stability problem of Rutherford's model.
Quote: Rutherford described the 1-in-12,000 rebound: "This result was almost as incredible as if you fire a 15-inch shell at a piece of tissue paper and it comes back and hits you."
• Atom is mostly empty space (most α passed through)
• Small, dense, positively charged nucleus exists at centre
• Nucleus size ~10⁻⁵ times the atom's radius
• Electrons revolve around nucleus in orbits
Key discovery: The atomic nucleus — revolutionised understanding of matter. Rutherford rightly called "father of nuclear physics."
Isotopes vs Isobars. ISOTOPES (left): Hydrogen has 3 isotopes — Protium (¹H, 1p, no neutron), Deuterium (²H, 1p+1n), Tritium (³H, 1p+2n). Same element (Z=1 for all) but different mass numbers. Same chemical properties, different physical properties. ISOBARS (right): Calcium (Z=20) and Argon (Z=18) — both have mass number 40 but are completely different elements with different chemical properties.
Cancer treatment: Cobalt-60 (⁶⁰Co) → gamma radiation → kills cancer cells (cobalt therapy)
Thyroid/Goitre treatment: Iodine-131 (¹³¹I) → treats thyroid disorders; Iodine-123 → thyroid imaging
Carbon dating: Carbon-14 (¹⁴C) → radioactive decay at known rate → dates organic materials up to 50,000 years old
Medical imaging: Technetium-99m (⁹⁹ᵐTc) → most widely used radioactive isotope in nuclear medicine; SPECT scans
Heavy water: Deuterium (²H) + Oxygen → D₂O (heavy water) → moderator in nuclear reactors
Archaeological dating: Uranium-238 → Lead-206 decay (half-life 4.47 billion years) → dates rocks
| Feature | Isotopes | Isobars |
|---|---|---|
| Atomic No. (Z) | Same | Different |
| Mass No. (A) | Different | Same |
| Element | Same element | Different elements |
| Protons | Same | Different |
| Neutrons | Different | Different |
| Chemical properties | Similar (same e⁻ config) | Different |
| Example | ¹²C and ¹⁴C (both carbon) | ⁴⁰Ca and ⁴⁰Ar |
1 u = 1/12 × mass of one C-12 atom
H = 1 u, C = 12 u, N = 14 u, O = 16 u, Na = 23 u, Mg = 24 u, Al = 27 u, S = 32 u, Cl = 35.5 u, Ca = 40 u, Fe = 56 u
Examples:
H₂O = 2(1) + 16 = 18 u
CO₂ = 12 + 2(16) = 44 u
H₂SO₄ = 2(1)+32+4(16) = 98 u
NaCl = 23+35.5 = 58.5 u
NH₃ = 14+3(1) = 17 u
Ca(OH)₂ = 40+2(16+1) = 74 u
No. of moles = Given mass ÷ Molar mass
No. of particles = Moles × 6.022 × 10²³
Example: 36 g of water = 36/18 = 2 moles = 2 × 6.022×10²³ = 1.204×10²⁴ molecules
Avogadro No. = 6.022 × 10²³ per mole
Monoatomic (1): Noble gases — He, Ne, Ar, Kr, Xe, Rn (exist as single atoms)
Diatomic (2): H₂, O₂, N₂, F₂, Cl₂, Br₂, I₂ (the "diatomic 7")
Triatomic (3): O₃ (ozone), H₂O, CO₂, SO₂
Tetraatomic (4): P₄ (white phosphorus), NH₃
Polyatomic: S₈ (sulphur — 8 atoms!), C₆₀ (Buckminsterfullerene)
Cation (+): Loses electrons → positive charge. Na⁺, Mg²⁺, Al³⁺, Ca²⁺, H⁺, NH₄⁺
Anion (−): Gains electrons → negative charge. Cl⁻, O²⁻, N³⁻, OH⁻, SO₄²⁻, CO₃²⁻
Polyatomic ion: Group of atoms with net charge. OH⁻ (hydroxide), SO₄²⁻ (sulphate), CO₃²⁻ (carbonate), NO₃⁻ (nitrate), PO₄³⁻ (phosphate), NH₄⁺ (ammonium)
1. Metal written first, non-metal second
2. Valencies must balance (cross-multiply)
3. Polyatomic ions get brackets if subscript > 1
Cross method examples:
MgO: Mg²⁺ and O²⁻ → valencies 2,2 → ratio 1:1 → MgO
AlCl₃: Al³⁺ and Cl⁻ → valencies 3,1 → ratio 1:3 → AlCl₃
Ca(OH)₂: Ca²⁺ and OH⁻ → valencies 2,1 → Ca takes 1 OH, OH gets 2 → Ca(OH)₂ (brackets because 2 OH groups)
Na₂SO₄: Na⁺ and SO₄²⁻ → valencies 1,2 → 2 Na needed → Na₂SO₄
Fe₂O₃: Fe³⁺ and O²⁻ → valencies 3,2 → cross = Fe₂O₃
- Most of the space inside an atom is empty, as most alpha particles passed straight through the gold foil.
- The positive charge and most of the mass of an atom are concentrated in a very small central region called the nucleus.
- Electrons revolve around the nucleus in fixed orbits with discrete energy levels, and do not radiate energy while in these orbits.
- a) 1 and 2 only ✓
- b) 2 and 3 only
- c) 1 and 3 only
- d) 1, 2 and 3
Statement 2 CORRECT — Rutherford's conclusion: A tiny fraction (~1 in 12,000) of alpha particles bounced back at large angles, including some nearly straight back. This could only happen if they encountered a very tiny but extremely dense, positively charged region — the nucleus. Rutherford calculated the nucleus radius is about 10⁻⁵ times the atom's radius (i.e., if an atom were the size of a football stadium, the nucleus would be the size of a marble).
Statement 3 WRONG — This is Bohr's postulate, NOT Rutherford's conclusion: Rutherford's model had electrons revolving around the nucleus, but Rutherford's model could NOT explain why electrons don't spiral in (they should lose energy by radiation). It was Niels Bohr (1913) who solved this by proposing that electrons exist in fixed orbits with discrete energy levels and do not radiate energy while in these specific orbits. Rutherford's experiment only proved the nuclear structure — the shell/energy level concept is entirely Bohr's contribution.
- (a) ¹²C has 6 protons and ¹⁴C has 8 protons — they are different elements despite similar names
- (b) Both have 6 protons (same element, same Z=6) but ¹²C has 6 neutrons while ¹⁴C has 8 neutrons — they have the same chemical properties but ¹⁴C is radioactive and used for carbon dating to determine the age of ancient organic materials
- (c) ¹²C and ¹⁴C have the same number of neutrons but different numbers of electrons — they have different chemical properties and belong to different periods of the periodic table
- (d) ¹⁴C has a higher atomic number than ¹²C — it was created artificially in nuclear reactors and does not occur naturally
- (a) The beaker contains exactly 1 mole of water molecules because the molar mass of water is 9 g/mol (hydrogen=1, oxygen=8, total=9)
- (b) The beaker contains 2 moles of water, giving 1.204 × 10²⁴ water molecules, because 9 g divided by the molar mass of 4.5 g/mol gives 2
- (c) The beaker contains 0.5 moles of water molecules (9 g ÷ 18 g/mol = 0.5 mol), which equals 0.5 × 6.022 × 10²³ = 3.011 × 10²³ water molecules; and since each H₂O has 2 hydrogen and 1 oxygen atom, it contains 6.022 × 10²³ hydrogen atoms and 3.011 × 10²³ oxygen atoms
- (d) The mole concept only applies to gases, not to liquids like water — so the mole calculation is not applicable here
- (a) Despite having the same mass number (40 nucleons in each nucleus), calcium and argon are completely different elements with entirely different chemical properties — calcium is a reactive metal (alkaline earth metal) that forms compounds, while argon is an inert noble gas that does not form compounds — because they have different atomic numbers (different numbers of protons and electrons), giving them completely different electron configurations and valencies
- (b) Since calcium and argon are isobars with the same mass number, they have similar chemical properties and can substitute for each other in chemical reactions — isobars behave like isotopes but for different elements
- (c) The isobar relationship means that calcium and argon are found together in nature because they have the same atomic weight — minerals containing calcium often also contain argon in equal proportions
- (d) Isobars cannot actually exist in nature — the mass numbers of different elements are always unique, so calcium (A=40) and argon (A=40) having the same mass number is a theoretical coincidence that has no practical significance
- (a) Lavoisier's discovery that mass is conserved in chemical reactions, which Dalton had not accounted for in his original theory
- (b) Proust's establishment of the Law of Definite Proportions, which showed that compounds always have fixed mass ratios — contradicting Dalton's assumption that atoms could combine in any ratio
- (c) Avogadro's hypothesis that equal volumes of gases at the same temperature and pressure contain equal numbers of molecules — which suggested gas molecules could be diatomic, challenging Dalton's view that elemental gases consist of single atoms
- (d) J.J. Thomson's discovery of the electron (1897), which proved that atoms ARE divisible into sub-atomic particles — directly contradicting Dalton's postulate that atoms are indivisible particles that cannot be created or destroyed
| Topic | Key Facts |
|---|---|
| Laws | Conservation of Mass (Lavoisier): mass neither created nor destroyed. Definite Proportions (Proust): elements in fixed mass ratios. H:O in water always = 1:8. 9g water → 1g H + 8g O. |
| Dalton's Theory (1808) | Atoms indivisible, same element identical, different elements different masses, combine in whole number ratios. Success: explains 2 laws. Failure: atoms ARE divisible (e⁻, p⁺, n discovered); isotopes disprove "same element = same mass." |
| Sub-atomic Particles | Electron (e⁻): Thomson 1897, charge −1, negligible mass. Proton (p⁺): Goldstein 1886, charge +1, mass ~1u. Neutron (n°): Chadwick 1932, charge 0, mass ~1u. Protons + neutrons in nucleus. Electrons in orbits. |
| Atomic Models | Thomson (plum pudding/watermelon): positive sphere + embedded electrons. ❌ Disproved by Rutherford. Rutherford (nuclear/gold foil): tiny dense positive nucleus + electrons in orbits. ❌ Electrons should spiral in. Bohr (shell model): fixed energy shells K/L/M/N (n=1/2/3/4), no radiation in orbit. ✅ Explains stability. |
| Gold Foil Experiment | α-particles at thin gold foil. Observations: most passed (atom mostly empty), some deflected (positive charge in small region), 1/12000 bounced back (tiny dense nucleus). Quote: "15-inch shell at tissue paper." |
| Bohr's Rules | Shell capacity = 2n². K(n=1)=2, L(n=2)=8, M(n=3)=18, N(n=4)=32. Outermost max = 8. Electrons fill shells step by step (inner first). Electrons in discrete orbits don't radiate energy. |
| Key numbers | Atomic No. Z = protons = electrons (neutral). Mass No. A = protons + neutrons. Neutrons = A − Z. Valency = electrons gained/lost/shared to complete octet (8). |
| Isotopes | Same Z, different A. Same chemical properties, different physical. H: Protium (¹H), Deuterium (²H), Tritium (³H). C: ¹²C and ¹⁴C. Cl: ³⁵Cl (75%) and ³⁷Cl (25%) → avg = 35.5. Applications: U-235 (nuclear reactor), Co-60 (cancer), I-131 (goitre), C-14 (dating), Tc-99m (medical imaging). |
| Isobars | Same A, different Z. Different elements, different chemical properties. Ca(Z=20, A=40) and Ar(Z=18, A=40). Completely different chemistry despite same nucleon count. |
| Mole Concept | 1 mole = 6.022 × 10²³ particles (Avogadro's number). Molar mass = molecular/atomic mass in grams. Moles = mass ÷ molar mass. H₂O: mol. mass=18g/mol. CO₂=44. NaCl=58.5. Ca(OH)₂=74. Defined by: atoms in 12g of C-12. |
| Valency | H=1, He=0, Li=1, Be=2, B=3, C=4, N=3, O=2, F=1, Ne=0, Na=1, Mg=2, Al=3, Si=4, P=3/5, S=2/4/6, Cl=1, Ar=0, Ca=2, Fe=2/3. |
Trap 1 — "Rutherford's model proposed electrons in fixed energy shells" → WRONG! Fixed energy shells / discrete orbits is BOHR's contribution (1913) — not Rutherford's. Rutherford's model (1911) had electrons simply revolving around the nucleus in orbits, but gave no explanation for why they don't spiral inward. Bohr (1913) solved this by proposing specific allowed orbits with discrete energies. Pattern Q above directly tests this distinction — Statement 3 attributes Bohr's idea to Rutherford and is WRONG.
Trap 2 — "Isotopes have similar chemical AND physical properties" → WRONG! Isotopes have similar CHEMICAL properties but DIFFERENT physical properties. Since chemical properties depend on electron configuration (same for isotopes — same Z), isotopes react similarly. But physical properties (mass, density, radioactivity, melting/boiling point) differ because the atoms have different masses. ¹²C (stable) and ¹⁴C (radioactive) — same chemistry, very different physics.
Trap 3 — "The atomic mass of Oxygen is 8" → WRONG! 8 is the ATOMIC NUMBER of Oxygen (number of protons). The ATOMIC MASS of Oxygen is 16 u. This is the most common calculation error. Molecular mass of water: H₂O = 2(1) + 16 = 18, NOT 2(1)+8=10. Always remember: atomic number Z=8 for O, atomic mass=16 for O. The confusion arises because there are 8 protons AND 8 neutrons in ¹⁶O → total 16.
Trap 4 — "Isobars have similar chemical properties like isotopes" → WRONG! Isobars have the SAME MASS NUMBER but COMPLETELY DIFFERENT chemical properties — because they are different elements with different atomic numbers (different electron configurations). Calcium (Z=20, reactive metal, valency 2) and Argon (Z=18, inert noble gas, valency 0) are isobars — their chemistry is utterly different. Isotopes share chemical properties; isobars do NOT.
Trap 5 — "Thomson discovered the proton; Goldstein discovered the electron" → WRONG! (Discovery roles confused) Thomson discovered the ELECTRON (1897) via cathode ray tube experiments. Goldstein discovered the PROTON (1886) via canal rays (positively charged rays moving toward the cathode). Chadwick discovered the NEUTRON (1932). These are often swapped in UPSC traps — remember the order: E-T-G-P (Thomson → Electron; Goldstein → Proton; Chadwick → Neutron) or "Thomson electrons, Goldstein Protons."


