CHAPTER

6 Thermodynamics

DEFINITION HEAT (q)

Deals with interaction of one body with another in terms of energy. Energy exchange due to temperature difference:
System: Part of universe under investigation.
Surrounding: Rest part of universe except system. q = CDT,
Boundary: Divide system & surrounding. q = nCmDT,
SYSTEM q = msDT
1. Open system: Can exchange matter and energy with
surrounding. WORK (W)
2. Closed system: Can exchange energy & not matter with
surroundings. Reversible Irreversible
3. Isolated system: Can neither exchange energy nor matter
with surrounding. V2

Wrev = – ∫ Pext .dV Wirr = –Pext (V2–V1)

STATE FUNCTION V1

Properties which depends only on initial & final state of system &
not on process or path. e.g. U, H, S, G, etc.
SIGN CONVENTION
PATH FUNCTION
Depends on path or process. e.g. work, heat.

THERMODYNAMIC PROPERTIES
1. Intensive: Independent of amount of substance, e.g. T,P Gas
viscosity, specific heat capacity, density, Boiling point, w = +ve w = –ve
freezing point, etc. Compression Expansion
2. Extensive: Depend upon amount of substances, e.g. mass,
volume, energy, entropy, enthalpy, internal energy, etc. ™ Heat absorbed by the system = q (+ve)
™ Heat evolved by the system = q (–ve)
PROCESSES ™ Work done on the system = w (+ve)
1. Isothermal: Temperature constant. ™ Work done by the system = w (–ve)
2. Isobaric: Pressure constant.
3. Isochoric: volume constant. INTERNAL ENERGY (E & U)
4. Adiabatic: Heat change constant. Every system having some quantity of matter is associated with a
5. Cyclic: Initial & final state of system are same. definite amount of energy called internal energy.
Reversible process Irreversible process U = UKinetic + UPotential + UElectronic + Unuclear + ........
™ Slow process ™ Fast process
™ At any time system ™ No equilibrium between FIRST LAW OF THERMODYNAMICS
and surrounding are in system and surrounding Law of conservation of energy
equilibrium. ™ Psys = Psurr ± DP
DU = q + W
™ Psys = Psurr ± dP
ENTHALPY
H = U + PV, DH = DU + (Dng) RT

Process Expression for w Expression for q Work on PV-graph

V2 V  P1
w = –nRT ln q = nRT ln  2 
Reversible V1  V1 

P (atm)
P2
isothermal P P 
= –nRT ln 1 q = nRT ln  1 
P2  P2 
V1 V2

P1
q=0
Reversible w = nCV(T2–T1) Isotherm
PVg = constant Adiabatic

P (atm)
adiabatic P V –PV P2
= 2 2 1 1 TVg–1 = constant
process γ –1
TP1–g/g = constant
V1 V2

STATEMENTS OF SECOND LAW OF VARIATION OF DSr WITH TEMPERATURE &

THERMODYNAMICS PRESSURE
(i) No cyclic engine is possible which take heat from one T2
(DSr)T – (DSr)T = (DCP)r ln
single source and in a cycle completely convert it into work 2 1 T1
without producing any change in surrounding. P1
(DSr)P – (DSr)P = DngR ln
2 1 P2
Source
Similarly
E w (DHr)T – (DHr)T = (DCP)r (T2–T1)  {Kirchoff's equation}
2 1
(DUr)T – (DUr)T = (DCV)r (T2–T1)
2 1
Sink
GIBBS FREE ENERGY (G) AND SPONTANEITY
(ii) In an irreversible process entropy of universe increases but A new thermodynamic state function G, the Gibbs free energy is
it remains constant in a reversible process. defined as:
DSsyst. + DSsurr = 0 for rev. process G = H – TS
DSsyst. + DSsurr > 0 for irrev. process at constant temperature and pressure
DSsyst. + DSsurr ≥ 0 (In general) DG = DH – T DS
If (DG)T,P < 0 Process is irreversible (spontaneous)
CALCULATION OF ENTROPY CHANGE FOR AN (DG)T,P = 0 Process is reversible
IDEAL GAS (DG)T,P > 0 Process is impossible (non
spontaneous)
General Expression
T2 V T P SOME FACTS TO BE REMEMBERED
DS = nCV ln + nR=
ln 2 nCP ln 2 + nR ln 1
T1 V1 T1 P2 (a) Standard condition
Reversible & irreversible isothermal expansion or contraction ™ For gases/solid/liquid
V P = 1 bar
of an ideal gas DS = nR ln 2 ™ For ion/substance in solution
V1
Concentration = 1M
THIRD LAW OF THERMODYNAMICS (b) DGr = (DGf)product – (DGf)reactant
“At absolute zero, the entropy of a perfectly crytalline substance is DHr = (DHf)product – (DHf)reactant
zero”. which means that at absolute zero every crystalline solid is DSr = (DSf)product – (DSf)reactant
in a state of perfect order and its entropy should be zero. (All above equation will be derived in thermochemistry)

P
W Chemical Thermodynamics and Energetics 15
THERMOCHEMISTRY
Bond Enthalpy
Average amount of enthalpy required to dissociate one mole
gaseous bond into separate gaseous atoms.
DrH = (Sum of bond enthalpy of gaseous reactant) – (Sum of bond
enthalpy of gaseous product)
Resonance Energy
∆H °resonance = DfH° (experimental) – DfH° (calculated)
    = DCH° (calculated) – DCH° (experimental)
Enthalpy Change
DH° = ∑H° (products) – ∑H° (reactants)
1. Enthalpy of reaction: The enthalpy change accompanying
a chemical reaction when the number of moles of reactants
reacts to give the products as given by the balanced chemical
equation.
2. Enthalpy of Combustion (DcH°): The amount of heat change
when 1 mole of substance is completely burnt in excess of
oxygen or air. DcH° is always negative.
3. Enthalpy of solution: The enthalpy change when one mole
of a substance is dissolved in large excess of solvent so that
further dilution does not give any further enthalpy change.
16
4. Enthalpy of hydration: The enthalpy change during the
hydration of 1 mole of anhydrous salt to a specific hydrate.
5. Enthalpy of neutralization (DHneut) Always exothermic:
Change in enthalpy when one gram equivalent of an acid is
completely neutralized by one g-equivalent of a base in dilute
solution.
SA + SB → salt + water ; DH°neut
H+(aq) + OH–(aq) → H2O(l) ; DH = –13.7 kCal eq–1 = –57.3 kJ eq–1
In case of weak acid/ base or both |DHN° | < 13.7 Kcal/eq–1 and
the difference is enthalpy of ionisation of weak species except
in case of HF when |DHN| > 13.7 Kcal/eq–1 due to hydration
of F–.
™ If in a reaction heat of reactant & products are given then heat
of that reaction can be measured as follows:
(a) For heat of combustion & for bond enthalpy
DrH = Σ(DHC)reactant – Σ (DHC)product
(b) For heat of formation
DrH = Σ(DHf)product – Σ (DHf)reactant
Hess’s Law: The enthalpy change in a particular reaction is the
same whether the reaction take place in one step or in a number
of steps.
JEE (XI) Module-2 PW