Chemical Thermodynamics Formula Sheet — JEE Main Chemistry
Every key Chemical Thermodynamics formula, definition and theorem for JEE Main Chemistry in one place — with common examiner traps and worked examples. Free to read; blurt from memory, then check your gaps.
Syllabus — topics coveredNTA · 15 sub-topics
Concepts of System and types of systems
Surroundings
Work, heat, energy
Extensive and intensive properties
State functions
First law of thermodynamics - internal energy and enthalpy
Heat capacity and specific heat
Measurement of ΔU and ΔH
Hess's law of constant heat summation
Enthalpy of bond dissociation, combustion, formation, atomization, sublimation, phase transition, ionization, solution and dilution
Second law of thermodynamics (brief introduction)
Introduction of entropy as a state function
Gibbs energy change for spontaneous and non-spontaneous processes
Criteria for equilibrium
Third law of thermodynamics (brief introduction)
Basic Concepts & First Law
Defining the system
▸System = part of the universe under study; surroundings = everything else; universe=system+surroundings.
▸Open: exchanges matter + energy (open beaker). Closed: energy only (sealed flask). Isolated: neither (thermos flask).
▸State functions (U, H, p, V, T, S, G) depend only on the state, not the path; q and w are path functions.
Internal energy (U): The total energy stored in a system (kinetic + potential + bond, etc.). It is a state function; only changes ΔU can be measured, not absolute values. ΔU depends on initial and final states alone.
Heat (q) and work (w)
▸Heat q: energy exchanged due to a temperature difference (random molecular motion).
▸Work w: ordered energy transfer; for gases, mainly pressure-volume work.
▸Adiabatic process: no heat exchange (q=0), so ΔU=wad.
Process
Held constant
Ideal-gas result
Isothermal
T
ΔU=ΔH=0, q=−w
Adiabatic
q=0
ΔU=w=nCVΔT
Isobaric
p
qp=ΔH=nCpΔT
Isochoric
V
w=0, qV=ΔU=nCVΔT
Cyclic
returns to start
ΔU=ΔH=0
Extensive vs intensive
▸Extensive (depend on amount, additive): mass, V, U, H, S, G, heat capacity C.
▸Intensive (independent of amount): T, p, density, molar/specific properties (Cm, ΔH per mole), refractive index. The ratio of two extensive properties is intensive.
Classify the system, then apply ΔU=q+w with the IUPAC sign convention.
First law of thermodynamics
ΔU=q+w
Energy of an isolated system is constant (q=w=0⇒ΔU=0). Sign convention: heat absorbed by the system and work done on the system are positive.
★ Remember · Sign convention (IUPAC)
q>0: heat flows into the system. w>0: work done on the system (compression). q<0 / w<0: system releases heat / does work on surroundings.
🎯 Exam · What thermodynamics does (and doesn't) tell you
It predicts whether a process is feasible and the energy involved, from initial and final states only — it says nothing about the rate (that is kinetics).
🚫 Examiner Trap · Examiner traps
(1) IUPAC sign: q>0 heat IN, w>0 work done ON the system ⇒ΔU=q+w (some books use ΔU=q−w — know which). (2) U,H,S,G are STATE functions; q,w are PATH functions. (3) Adiabatic q=0⇒ΔU=w. (4) Thermodynamics gives feasibility, NOT rate (that's kinetics).
Work, Enthalpy & Heat Capacity
Irreversible (const. pex)
w=−pexΔV
Reversible isothermal
w=−2.303nRTlogV1V2
Free expansion (pex=0)
w=0
Const. volume (ΔV=0)
ΔU=qV
Work = area under the p–V curve; reversible work is the maximum.
Enthalpy (H): The heat content at constant pressure: H=U+pV. Since most reactions occur in open vessels at constant atmospheric pressure, ΔH=qp (heat exchanged at constant p). H is a state function.
Relating ΔH and ΔU
ΔH=ΔU+ΔngRT
Δng = (moles of gaseous products) − (moles of gaseous reactants). For reactions with no gas change or only solids/liquids, ΔH≈ΔU.
Bomb calorimeter measures qV=ΔU (constant volume, no work). Coffee-cup (constant p) measures qp=ΔH. Heat lost by reaction = heat gained by calorimeter =mcΔT.
🚫 Examiner Trap · Examiner traps
(1) w=−pexΔV: on expansion (ΔV>0) work is negative (system does work). (2) Reversible work is the MAXIMUM magnitude; free expansion (pex=0) gives w=0. (3) ΔH=ΔU+ΔngRT — use Δng of gas moles only. (4) Bomb calorimeter measures qV=ΔU; coffee-cup qp=ΔH.
Thermochemistry — Enthalpy Types
Standard reaction enthalpy (ΔrH⊖): The enthalpy change of a reaction when all reactants and products are in their standard states (pure form at 1 bar, data usually at 298 K). The ⊖ superscript denotes standard conditions.
▸Coefficients = moles (not molecules); ΔrH has units kJ mol−1 (per mole of reaction).
▸Reverse the reaction ⇒ reverse the sign of ΔH.
▸Multiply coefficients by n ⇒ multiply ΔH by n (enthalpy is extensive).
Enthalpy of
Symbol
Process
Formation
ΔfH⊖
1 mol compound from elements
Combustion
ΔcH⊖
1 mol burnt in excess O2
Atomization
ΔaH⊖
1 mol → gaseous atoms
Fusion
ΔfusH⊖
solid → liquid
Vaporization
ΔvapH⊖
liquid → gas
Sublimation
ΔsubH⊖
solid → gas
Solution
ΔsolH⊖
1 mol dissolved
★ Remember · Standard enthalpy of formation
ΔfH⊖ of an element in its reference state (e.g. O2(g), C(graphite), H2(g)) is taken as zero. ΔsubH=ΔfusH+ΔvapH (state-function additivity).
🎯 Exam · Solution = lattice + hydration
ΔsolH⊖=ΔlatticeH⊖+ΔhydH⊖. Fusion, vaporization, sublimation are always endothermic (+).
More named enthalpies (syllabus list)
▸Bond dissociation: break 1 mol of a bond in the gas phase (always +).
▸Hydration: 1 mol of gaseous ions into water (always −).
▸Ionisation (of a weak electrolyte): energy to ionise it fully in solution. Neutralisation of a strong acid by a strong base is −57.1kJ/mol (just H++OH−→H2O); with a WEAK acid or base it is less negative, the difference being the ionisation enthalpy.
▸Resonance energy=ΔHobserved−ΔHcalculated (from bond enthalpies of one Lewis structure); e.g. benzene is more stable than the Kekulé estimate.
🚫 Examiner Trap · Examiner traps
(1) ΔfH⊖ of an element in its reference state is zero (O2, C-graphite, H2). (2) Reverse a reaction ⇒ flip the sign; multiply coefficients ⇒ multiply ΔH (extensive). (3) Fusion/vaporisation/sublimation are always endothermic (+). (4) ΔsubH=ΔfusH+ΔvapH.
Hess's Law & Bond Enthalpy
Hess's law of constant heat summation: If a reaction occurs in several steps, its overall enthalpy change is the sum of the enthalpy changes of the steps — because enthalpy is a state function (path-independent).
Direct ΔrH = sum along any indirect route (ΔH1+ΔH2+ΔH3).
From formation enthalpies
ΔrH⊖=∑aiΔfH⊖(products)−∑biΔfH⊖(reactants)
ai,bi = stoichiometric coefficients. 'Products minus reactants.'
From bond enthalpies (gas phase)
ΔrH⊖=∑B.E.(bonds broken)−∑B.E.(bonds formed)
'Reactant bonds − product bonds.' Valid only when all species are gaseous. For diatomics, bond enthalpy = bond dissociation enthalpy; for polyatomics use mean bond enthalpy (e.g. mean C–H in CH4=416 kJ mol−1).
🎯 Exam · Born–Haber cycle (lattice enthalpy)
Lattice enthalpy can't be measured directly, so it is found by a Hess cycle: ΔfH=ΔsubH+21ΔbondH+ΔiH+ΔegH−ΔlatticeH (NaCl). The sum of all enthalpy changes around the closed cycle is zero.
✎ Example · Hess's law in action
Given C(s)+O2→CO2,ΔH=−393.5 and CO+21O2→CO2,ΔH=−283.0 kJ. Find ΔH for C+21O2→CO.
Target = (reaction 1) − (reaction 2).
ΔH=−393.5−(−283.0).
∴ ΔH=−110.5kJ mol−1.
🚫 Examiner Trap · Examiner traps
(1) From formation: products−reactants. From bond enthalpy: bonds broken−bonds formed (reactants − products) — OPPOSITE order, easy to flip. (2) Bond-enthalpy method needs ALL species gaseous. (3) Use mean bond enthalpy for polyatomics. (4) Born–Haber: lattice enthalpy from a closed Hess cycle (can't measure directly).
Spontaneity, Entropy & the Second Law
Spontaneous process: A process with the potential to proceed on its own without external help. It is irreversible and can only be reversed by an external agency. Spontaneity says nothing about the rate (e.g. H2+O2 is spontaneous but slow).
⚠️ Watch out · Enthalpy decrease is NOT the sole criterion
Many endothermic reactions are spontaneous (e.g. N2+O2→2NO,ΔH>0). So ΔH<0 alone cannot decide spontaneity — entropy must be included.
Entropy rises with disorder: Sgas>Sliquid>Ssolid.
Entropy (S): A state function measuring the degree of randomness or disorder of a system. For a reversible change at temperature T, ΔS=qrev/T (units J K−1 mol−1).
Second law of thermodynamics
ΔStotal=ΔSsys+ΔSsurr>0(spontaneous)
ΔStotal>0 for any spontaneous (irreversible) change; ΔStotal=0 at equilibrium. The entropy of the universe always increases.
Predicting the sign of ΔS
▸Increases (+): solid → liquid → gas, dissolving, more gas moles in products, mixing.
▸Decreases (−): gas → liquid/solid, fewer gas moles, association/ordering.
▸ΔSsurr=−TΔHsys — an exothermic reaction raises the surroundings' entropy.
phase change at its transition temperature (melting, boiling); ideal gas at constant T. Heating at constant p: ΔS=nCplnT1T2. Kirchhoff (not named in the syllabus): ΔHT2=ΔHT1+ΔCp(T2−T1)
🚫 Examiner Trap · Examiner traps
(1) ΔH<0 alone does NOT decide spontaneity — endothermic spontaneous reactions exist (entropy-driven). (2) Sgas>Sliquid>Ssolid; more gas moles ⇒ΔS>0. (3) ΔSsurr=−ΔHsys/T. (4) Second law: ΔStotal>0 for spontaneous, =0 at equilibrium — use the TOTAL, not just the system.
Gibbs Energy & Spontaneity
Gibbs energy (G): G=H−TS, an extensive state function. ΔG is the maximum useful (non-expansion) work a process can deliver at constant T and p — the 'free energy' of the reaction.
Gibbs–Helmholtz equation
ΔG=ΔH−TΔS
Combines the enthalpy (ΔH) and entropy (TΔS) drives into one spontaneity criterion at constant T,p.
★ Remember · The single criterion for spontaneity
ΔG<0: spontaneous (exergonic). ΔG=0: equilibrium. ΔG>0: non-spontaneous (the reverse is spontaneous).
Slope =−ΔS; the line crosses ΔG=0 at T=ΔH/ΔS.
ΔH
ΔS
Spontaneous?
−
+
Yes, at all T
−
−
Yes, at low T
+
+
Yes, at high T
+
−
No, at any T
🎯 Exam · Crossover temperature
When ΔH and ΔS have the same sign, spontaneity flips at T=ΔSΔH (where ΔG=0). This is why some reactions need heating (or cooling) to 'switch on'.
🚫 Examiner Trap · Examiner traps
(1) ΔG=ΔH−TΔS is the single criterion: <0 spontaneous, =0 equilibrium, >0 non-spontaneous. (2) Same-sign ΔH,ΔS⇒ spontaneity flips at T=ΔH/ΔS. (3) Watch UNITS — ΔS in J/K but ΔH in kJ (convert!). (4) ΔG is the max NON-expansion (useful) work.
Gibbs Energy & Equilibrium
Gibbs energy and equilibrium constant
ΔrG⊖=−RTlnK=−2.303RTlogK
At equilibrium ΔrG=0. This links thermodynamics to the position of equilibrium K.
Reading ΔrG⊖ and K
▸ΔrG⊖<0⇒K>1: products favoured (strongly exothermic reactions tend to have large K).
▸ΔrG⊖=0⇒K=1: reactants and products balanced.
▸ΔrG⊖>0⇒K<1: reactants favoured (strongly endothermic reactions form little product).
Combining both standard relations
ΔrG⊖=ΔrH⊖−TΔrS⊖=−2.303RTlogK
Lets you find K from calorimetric ΔH⊖ and ΔS⊖ — entropy can make K large even when ΔH>0 at high T.
🎯 Exam · Master checklist
Spontaneity ⇔ΔG<0⇔ΔStotal>0⇔K>1 (for ΔrG⊖). Use ΔH (energy) and TΔS (disorder) together — never ΔH alone.
✎ Example · Is the reaction spontaneous?
For a reaction ΔH=+30 kJ mol−1, ΔS=+100 J K−1 mol−1. Find the temperature above which it becomes spontaneous.
Spontaneous when ΔG=ΔH−TΔS<0.
Crossover at T=ΔSΔH=10030000.
∴ T>300K (above 300 K, ΔG<0).
🚫 Examiner Trap · Examiner traps
(1) ΔrG⊖=−RTlnK: ΔrG⊖<0⇒K>1 (products). (2) ΔrG⊖ (standard) decides K; ΔrG (actual) decides direction NOW — don't confuse. (3) Even ΔH>0 can give large K at high T if ΔS>0. (4) At equilibrium ΔrG=0, NOT ΔrG⊖=0.
What are the most important Chemical Thermodynamics formulas for JEE Main?
This Chemical Thermodynamics formula sheet covers all the high-yield Chemistry formulas, definitions and theorems you need for JEE Main, across Concepts of System and types of systems, Surroundings, Work, heat, energy, Extensive and intensive properties, State functions — each shown with the key result and, where useful, a worked example.
Is this Chemical Thermodynamics formula sheet free?
Yes — the full chapter formula sheet is free to read online, no login or payment required.
How should I revise Chemical Thermodynamics formulas?
Blurt the Chemical Thermodynamics formulas from memory, then check against this sheet to find your gaps — and practise a few previous-year questions on the chapter to make sure you can apply them under time pressure.