THERMODYNAMICS

PROCESSES THERMODYNAMICS
PROPERTIES
THERMODYNAMICS GIBB'S FREE ENERGY
• Isothermal Process INTENSIVE PROPERTIES
dt = -, ∆U = 0 EXTENSIVE PROPERTIES
P, T, N V, U, H ZEROTH LAW OF THERMODYNAMICS The net energy available to do useful work and is a measure of 'free
• Isochoric Process Properties of the system Properties of the system energy'.
∆V = 0 which only depend on the which depend on the path If two thermodynamics
nature of matter of the system A states are in thermal Standard free energy of a reaction: ∆rG° = Σ∆ f G°products − Σ∆ f G oreac tan ts
• Adiabatic Process STATE FUNCTION PATH FUNCTION equilibrium with a third
∆q = 0 ∆U, ∆H, ∆G HEAT WORK one, then they are in Gibb ' s − Helmholtz equation ∆G° = ∆H° − T∆s°∆G° = nFEocell
Properties of the system Properties of the system thermal equilibrium
• Cyclic Process which only depend on the which depend on the path A A
∆Ucyclic = 0 nature of matter of the system with each other.
GIBB'S ENERGY CHANGE
DG < 0, rocess is spontaneous
& EQUILIBRIUM
TYPES OF SYSTEM ∆rG° = −2.303RT log K DG > 0, rocess is non-spontaneous

OPEN SYSTEM CLOSED SYSTEM ∆G° = 0 log K = 0 Equilibrium reached DG < 0, rocess is equilibrium
Universe
Surroundings ∆G° < 0 log K > 0 Mixture contains
Matter sYSTEM log K < 0 products
Matter
∆G° > 0 Mixture contains
Energy Energy reactants Sign of Sign of ∆ G = ∆ H − T∆ s Equilibrium reached
∆H ∆S
Always
ISOLATED SYSTEM Negative Positive Spontaneous at all temp
Negative
Expansion: Vi > Vf Always Non-spontaneous at all
Positive Negative
Matter
Compression: Vf < Vi Negative temperature
Non-spontaneous at all
Energy +ve @ low temp.
temperature
Postive Postive
spontaneous at high
-ve @ low temp.
temperature
w pv = − p ext ∆V
ISOTHERMAL -ve @ low temp. spontaneous at low
temperature
ISOTHERMAL REVERSIBLE
Negative Negative
spontaneous at low
+ve @ low temp.
ENTHALPY v
IRREVERSIBLE w = −2.303nRT log  v
rev
2 

temperature

∆H = ∆U + ∆(pV)
HEAT CAPACITY WORK
1 

∆H = ∆U + ∆ngRT Amount of heat required to raise the

INTERNAL WORK (W) nR ADIABATIC
Enthalpy of reaction (∆nrH) temperature of a system by 1°C.
Molar heat capacity 1°C.
HEAT (Q) w rev = (T − T1 )
r−1 2 IRREVERSIBLE SPONTANEITY
Reactants → Products ENERGY When there is difference
Molar heat capacity ⇒ q = nc∆T ADIABATIC
∆ r H = e∑ a i H products − ∑ b i H reactants Exchange of energy  p T − p 2 T2 
w irrev = − p ext R  1 1
Total energy within between presence of the REVERSIBLE  p1p2


i i Specific heat capacity ⇒ q = mc∆T due to temperature
the substance system and surroundings,
differnece.
STANDARD ENTHALPY POISSON'S the work done is known as
MEYERS'S Wpv
OF REACTIONS (∆H°) FORMULA RATIO FREE EXPANSION
Cp
Standard enthalpy of fusion =∆fusH°
Cp - Cv = R =r When an ideal gas expands in vacuum

Standard enthalpy of phase change

Cv FIRST LAW OF then, pext = 0.
THERMODYNAMICS ∴ W=0
∆fusH°, ∆vapH°, ∆SUBH°
Standard enthalpy of combustion ∆cH°
ENTROPY
Law of conservation of energy total energy of an isolated
Standard enthalpy = ∆bondH° EORN HABER CYCLE system is constant. SECOND LAW OF This is the measure of the degree of
randomness or disorder of the system.
Lattice enthalpy = ∆latticeH° Na+ (g) + Cl (g) Mathematically, ∆u= q + w THERMODYNAMICS q rev
∆s =
12∆ bond H° The entropy of the universe is always T(Reversible Process)
HESS' LAW CONSTANT + 1
SIGN increasing in the course of every s
∆s Total = ∆S syestem + ∆s surroundings
na (g) + Cl(g) ∆egH°
HEAT SUMMATION 2 CONVENTION pontaneous or natural change.
∆iH° At constant volume Entropy changes during phase transformation
Heat absorbed by the
∆u = qv
∆rH
na+ (g) +
1 Na+ (g) + Cl- (g) system = +ve CALORIMETRY ∆ fusion H ∆ H
A B
2
Cl(g)
At constant pressure THIRD LAW OF ∆ fusion S =
Tm
, ∆ vap s = ∆ vap S = vap
Tm
Heat evolved by the
∆rH1 ∆rH3
∆subH°
system = -ve ∆H = qp
(∆U) = Cv × ∆T × m THERMODYNAMICS
1 ∆LatticeH° ∆ subs H
∆rH2
na+ (s) + Cl(g) Work done by the The Entropy of a perfectly crystalline ∆ sub S =
C D
2
∆fH°
system = -ve (∆U) = Cv × ∆T × m substance at 0K or absolute zero is taken Tm
to be zero.
Work done on the T ∆ r S° = Σs°products − Σs°reactants
∆S = ∫ C p d ln T
∆rH = ∆rH1 + ∆rH2 + ∆rH3 NaCl(s) system = +ve 0