THERMODYNAMICS

THERMODYNAMICS PROPERTIES
PROCESSES
Isothermal Process INTENSIVE PROPERTIES EXTENSIVE PROPERTIES THERMODYNAMICS AKANSHA KARNWAL
ΔT = 0 P, T, N V, U, H
ZEROTH LAW OF THERMODYNAMICS
Isochoric Process Properties of the system Properties of the system GIBB'S ENERGY CHANGE
which are indepentent of which depend on the amount GIBB'S FREE ENERGY & EQUILIBRIUM
ΔV = 0 If two bodies are in
amount of system. of the system. A
Adiabatic Process STATE FUNCTION PATH FUNCTION
thermal equilibrium with The net energy available to do ΔG° = −2.303RT log K
q=0 Values of such functions Values of such functions a third one, then they useful work and it is a measure ΔG° = 0 log K = 0 Equilibrium reached.
do not depend on the path depend on the path of the are in thermal of spontanity.
Cyclic Process ΔG° < 0 log K > 1 Mixture contains
of the system. system. A A equilibrium with each
ΔU cyclic = 0 ΔG°= ΣΔG°Products −ΣΔG°Reactants mostly products.
e.g. ΔU, ΔH, ΔS etc. e.g. W and q other.
ΔG° > 0 log K < 1 Mixture contains
ΔG° = ΔH° - TΔS° mostly reactants.
TYPES OF SYSTEM
ΔG < 0, Process is spontaneous ΔG > 0, Process is non-spontaneous
OPEN SYSTEM ENTHALPY ΔG = 0, Process is at equilibrium
CLOSED SYSTEM
Matter
Energy
ΔH = ΔU + Δ(PV) Sign of Sign of
ISOTHERMAL IRREVERSIBLE ΔG = ΔH − TΔs Spontanity
Energy ΔH = ΔU + Δng RT WORK ΔH ΔS
Wirr= -Pext ΔV Negative Positive Always Negative Spontaneous at all temp.
ISOLATED SYSTEM Enthalpy of reaction (ΔH) ISOTHERMAL REVERSIBLE Positive Negative Always Positive Non-spontaneous at all temperature.

Matter ΔH = ΣΔH f(Products) - ΣΔH f(Reactants W

rev ( )
= -2.303nRT log
V2
V1 +ve @ low temp. Non-spontaneous at all temperature.
Positive Positive
Energy ΔH = ΣB.E. Reactants - ΣΒ.Ε Products W = -2.303nRT log (
rev ) P1
P2
-ve @ low temp. Spontaneous at high temperature.

ADIABATIC REVERSIBLE -ve @ low temp. Non-spontaneous at all temperature.

Enthalpy of fusion (ΔH°) Enthalpy change when 1 mole of compound undergoes melting at nR (T2-T1) Negative Negative
H O(s)→H O(l)
f Wre = +ve @ low temp. Spontaneous at high temperature.
2 2 constant temperature and atmospheric pressure. γR
Enthalpy of vapourization (ΔH° ) Enthalpy change when 1 mole of compound undergoes boiling at ENTROPY
vap
H O(l)→H O(g) constant temperature and atmospheric pressure. INTERNAL
2 2
HEAT (q) WORK (W) This is the measure of the degree of
Enthalpy of Sublimation (ΔH°sub ) Enthalpy change when 1 mole of solid substance is directly ENERGY (U) SPONTANEITY randomness or disorder of the system.
converted into gaseous state at a constant temperature and Work is a mode of energy
CO2 (s)→CO2 (g) Exchange of energy
standard pressure. Total energy within transfer when It is natural direction of a process. Δs =
q rev
due to temperature T
Enthalpy of Solution (ΔH°sol ) the substance temperature difference
Enthalpy change when 1 mole of substance is dissolved in fixed differnece.
KCl + aq→KCl (aq) quantity of solvent.
is not involved. ΔS =ΔS + ΔS
W = -PextΔV Total system surroundings
Bond dissociation enthalpy (Β.Ε.) It is the enthalpy change to break 1 mole bonds of a particular kind. FIRST LAW OF THERMODYNAMICS Entropy changes during phase transformation
Cl2 (g)→ 2Cl(g)
Law of conservation of energy total energy of an isolated
FREE EXPANSION ΔS fusion = ΔHfusion
, ΔS = ΔH vap
T vap T
HESS' LAW CONSTANT HEAT system is constant. When an ideal gas expands in vacuum then, pext= 0.
EORN HABER CYCLE

Molar HEAT CAPACITY Na+ (g) + Cl (g) Δ vap H

SUMMATION
Mathematically, Δu= q + w
∴ W=0 Δ
vap
S =
T
Amount of heat required to raise the
ΔH1 Na+(g) + 1 Cl(g) THIRD LAW OF Entropy change of a reaction.
temperature of a 1 mole substance.
A B SIGN CONVENTION
Molar heat capacity ⇒ qv = NvRT
2 -
Na+ (g) + Cl (g) SECOND LAW OF THERMODYNAMICS THERMODYNAMICS Δr S° = Σs°products − Σs°reactants
Specific heat capacity⇒ qp = nCpRT
+
Na (g) + 1 Cl(g) Heat absorbed by the Work done by the The Total entropy of the universe is always

akanshakarnwal_
ΔH ΔH = ΔH + ΔH + ΔH
1 2 3 ΔH2 2 system = -ve The Entropy of a perfectly crystalline
POISSON'S system = +ve increasing in the course of every spontaneous
MEYERS'S
RATIO Na+(s) + 1 Cl(g) substance at 0 K or absolute zero
FORMULA or natural change.
Cp - Cv = R
C p =γ D C 2 Heat evolved by the Work done on the
Temperature to be zero.
Cv ΔH3 NaCl(s) system = -ve system = +ve ΔS Total> 0