CLASS XI THERMODYNAMICS

THERMODYNAMICS SANDESH ARORA

2023 DPS NOIDA Sandesh Arora
1
Thermodynamlcs - Branch of chemlstry which deals with the energy changes in a chemical
reaction
2
Importance
a. Predicts feaslblity of a
chemlcal
b. Helps formulate conditlons for reaction
chemlcal reaction
Limitation -Falls to predict the speed of
Exothermic R. - Energy ls released whilereaction and mechanism of reaction
In endothermic reaction energy is absorbed
Types of Systems
Closed system Open system
Exchange of only energy Isolated system
(not mass) Exchange of both energy No exchange of energy
and matter and matter
State functions- are properties that are
dependent on only initial and final state of system
State variable - are properties which describe the system
P,V,T,H(Enthalpy ),S (Entropy),G ( Gibbes Free Energy)
Extensive properties -are properties which depend upon quantity of matter
Mass, mole, volume, enthalpy, heat capacity, free
Intensive properties -do not depend on quantityenergy of matter
Boiling point, temp, M, molarity, refractive index, specific heat capacity
Temperature
Is measure of degree of hotness and coldness
Heat
The energy exchanged between surrounding and system when their temp
are different
Exothermic Process
" The process in which heat is given out to the
surroundings.
" Products are more stable (at lower energy) than
10 reactants
Isothermal Process
Process in which temp of the system remains constant
11
Adiabatic process
Process in which no heat exchange takes place
12 Isolated system
No exchange of heat and matter
13 Reversible process
ldeal process carried out In infinite no of steps
14 Zeroth law
When C is in thermal equilbrium with A and B both, then A and B are also in thermal
each other equilibrium with
15 First Law of thermodynamics
Energy can neither be created nor be destroyed Mathematical Expression
AU= q+ w
AU =Internal Echange q= heat WE WOrk done
16 Molar heat capacity
Amount of heat required to raise temp of a body 1 mole in magnitude by 1K or 1 C

Heat capacity Molar Heat Capacity Specific heat Capacity

Amount of heat required to raise Amount of heat required to raise Amount of heat required to
temp of a body of any amount in ternp of a body 1 mole in raise temp of one unit mass by
magnitude by 1K or 1 C magnitude by 1K or 1 C 1 degree
(1Kelvin or 1 Celsius )
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 THERMODYNAMICS
CLASS XI
" Specific Heat Capacity
qheat gained or lost m ATchange in temp

17 Internal energy
" Is sum of all forms of energy that a system can posSsess
For isothermal process AU = zero
Absolute value cannot be measured
AU =2Uproduct Urouctant
AU= - Ve exothermic process
18
Enthalpy H- is defined as the total heat content of system. It is equal to the sum of
internal energy and pressure volume work
H =U+ pV
AH= 2Hproduct Hronctant
AH= AU + PAV
AH AU+ Ang RT
Ang= No of moles of gaseous
product- No of moles of gaseous reactant
19
Enthalpy of formation AHF
Enthalpy change accompanying the formation of one mole of the
elements compound from its
2C+3H2 + hO2 ’CHsOH
Elements
20 Standard
andard Enthalpy of formation
When all substances are in their
standard state
Note - Standard state 250 C
21
Enthalpy of reaction ’ 1 atm
Enthalpy change when reactants have reacted
22
CaH4 + H2 ’ CaHe completely in the given reaction
Enthalpy of combustion
Enthalpy change when one mole of
substance is completely oxidised (excess of Oz)
CH4 + 202’ Coz + 2H20
23
Hess's Law of constant heat
It states that the summation
enthalpy of reaction
out in single step or multiple steps remains the same whether the reaction is carried
AH 393 KJ
C+%Oz’ CO AH =110KJ
CO+ %O2’ COz
AH2=-283KJ
C+0> cO A+BAH= AH, +AH2
393 KJ
24
Thermodynamical equation-A balanced equation together with value
reactants + products of AH and physical state of
" Conversions regarding thermochemical equation
Coefficients in balanced thermochemical eq refer to no of moles (fractions are acceptable)
When Chemical Eq is reversed, AH is reversed in sign
Example
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 S XI
+3H2’2NHs AH=-91.8 KJ/mol THERMODYNAMICS SANDESH ARORA
ONHs> N2+ 3H2 AH = +91.3 KJ/mol
ohvslcal state of all specles must be specifled
Thermochemlcal equatlon can be added and subtracted
ORN HABER CYCLE

Born Haber Cycle

M(s) + 112 X2(g) AH MX()

AHublimation AHdissocintion
M) Xg) Lattice Energy ( )

Ionization Energy (TE)| |Electron Affiity (EA)

M) + X-(R)

AH0 AHub + IE + AHdiss + EA + U

Sandesh Arora
THERMODYNAMICS

Two riterias of spontaneous process

Tendency to acquire
Minimum energy
" Minimum disorder
randomnessEntropy
2 Thermodynamics representation of
disorder of a system
EntroPy is meaure of randomness or
Factors effecting randomness
a. Physical State
least)
Solid(molecules are held-tightly randomness
solld <Iiquid < gas
b. Temperature
randomness
temp a Kinetic energy a
G. Complextty
greater disorder
Sz >Ss (greater complexity)
d. Disselution
disorder increases
NaCl (solid) ’ NaCI (aqueous)
e. Chemical decompositlon

CaCO3CaO +COz randomness increases

partieles randomness inreases
f. Intermixing of inereases
presSure released volume randomness
g. VaCuum gas under

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 CLASS XI THERMODYNAMICS
Randomness Increases AS +ve entropy increases
1) Stretched rubber band ’ loose rubber band
2) Dry lce (solld CO) ’ Co2 gas
3) S -S
4)
5)
Protein (helical form) ’ Protein (Random coil form)
Crystalline solid OK ’ 110K
6)
2NaHC0,’ NaCO, +C02 +H20
7) Hz’ 2H
8) Hg
9)
(liquid) ’ Hg (gas)
AgNO, (solid) ’ AgNOs
10) H20 (solid) ’ H20 (aqueous)
10) Water’ steam (aqueous)
11) Gr(H20)6 3+’ Cr 3+ +
12) Glamond > 6H20
13) 2 (solid) ’ Cgraphlte
2
5
(gas)
Entropy - is a
Systemn
AS =
thermodynamical property which measures randomness or diorder of a
Sproduct -) Sreactant
AS = qrev /T = AHT

Cyclic process AS =zero

Equilibrium state AS= zero
6
First Law of
Thermodynamlcs
Law of
conservation of Energy
Second Law of thermodyamics
All spontaneous process or
naturally occuring processes are
irreversible
Or
thermodynamically
The entropy of universe is continuosly increasing
AS system+ AS surrounding > 0
7 Third law.
Entropy of a perfectlycrystalline substance is zero at OK
8 Gibbs Free Energy
Denoted by G
Predicts the direction of spontaneity
Defined as the energy available for doing useful work under condition of constant
P and temp.
Relation between EnthalpPy and entropy with Gibbs free energy
Gglbbs freo onorgy = Henthalpy - T Sentrop

10 Change in gibbs free Energy is useful in prediciting the direction of spontaneity

Gibbs Helmholtz Eq

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 SANDESH ARORA
THERMODYNAMICS

-ve spontaneous process

at equilbrium sGeo

Ataximum Useful Work AG -Wmax

eavanic cell - Gibbs free enrgy change is related to electrical work

AG = nF Eeell

standard state of reactant and products

n= No of moles of electrons
F=Faraday Charge carried by 1 mole of electron

43 Gibbs Energy change and equilibrium constant

AG =-2.303 RT Iog Kc

14 Standard free energy of formation

AG = ArGproduct AGreactant

= zero
AG of all pure element
spontaneity important
15 Effect of temp on
AG = AH -TAS

0= AH- TAS
0
At eg AG =
equilibrium
T= AHAS
temp T system at
spontaneous
becomes -ve thus reaction is
value of aG
Above temp T the
spontaneity
Effect of temperature on
16
AG Spontaneity
AH AS Depends on
- with high temp
+ temperature
+ with low temp
+
endothermic disorder Never

endothermic order
Always
+

exothermic disorder
with low temp Depends on
temperature
exothermic order + with high temnp

ArG Feasibility
ArH 5TPage ArS
 THERMODYNAMICS
CLASS XI

Temperature
+ve ve
Temperature
Ve
ve

Low temp > Temperature

+ve
High temp ’
+ve
Low temp >
Temperature
High temp>
Formulae=
" R
8.314 JK-1 mol
1dm 1lit
1lit atm = 101.3 J
p AH
AU = g+ w
First Law of Thermodynamics :mathematical form of first law
of thermodynamics
AU = 0
isothermal expansion
AH = AU + P AV
AH = AU + Ang RT

Important Formula
ArH = Aproduct
}AreactanH,
AS q/T = AH/IT
AG AH - TAS

T = AH I AS above this temp reaction becomes feasible

AG = - nFEell

AG= -2.303 RT log Kc

ArG = A, G product- }A, G reactant

Numericas
Enthalpy of combustion of gas Az and Ba are-1667.6 and -258.9 KJ. If both gasesform oxide A:0and
B20 and their atomic masses are 15 and 1 respectively whichis a better Rocket -fuel if equal masses
of both are used

2 Acylinder of cooking gas us assumed to contain 11.2 Kg of butane. The enthalpy ofcombustion of
is -2658 KJ. If famlly needs 15000 KJ of energy per day for cooking. How long would cylinder
last?

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 THERMODYNAMICS SANDESH ARORA
ASSNI
alcutato,Enthalpy of formation of CO glven
C, + Oz(9) ’ co:(g) AH -393.5 KJ
|cO(g) + , O(g)’ CO:(g) ArH -282.2 KJ

eulate Gibbs free energy change (standard) ,PCis(g) PCh(g) +Clh(g) at 25G
1.8x109
When Kc =
Ans = 38.5 KJ

Determine whether or not it is possible for sodium to reduce Al,0, to Al at 298K given
AG Alz0 1582 KJimol
AG Na20 -377 KJimol
Cus) + 2Ag'aq ’Cu2 + 2Ag
Calculate Gibbs free energy change (standard)
Ecell =0.46V AG= -88780J
6
What is equilibrium constant at 400K , 2NOCI(g) 2NO(g) + Clz(g)
given AH = 77.2 KJ/mol , AS = 122 JIK
-3.7081, Kc = 1.95x104
Ans ; AG = 28400, logk= monoxide. What heat change at
for combustion of carbon
7 Calculate useful work
constant pressure = -283 KJ at 298K given
So2=205.0 JIKmol
Scoz = 214 JIKmol, Sco = 197.9 JIKmol,

Ans = AS = -87 JIK, AG-257 KJ at

= 44 JIK and heat change
feasibility 2A(g) + B(g) ’ 2D(g) Entropy change Ans AH=13KJ AG = 0.164KJ
Predict
constant PresSure = -10.5 KJ equilibrium constant for
standard Gibbs free energy change at 300K when
Calculate
reaction is 10
Pb(s) + C) > Pbs) + COig) becomes feasible given AH = 108.4 KJimol
AS =
reaction
10 Calculate temp above which
190 JIKmol change for
formation Fe203(s) is -824.2KJ/mol. Calculate the enthalpy
1 The enthalpy of
the reaction Ans =1648.4KJ
4Fe(s) + 302(g) ’2 Fe20(s) entropy in - Evaporation of water, Boiling of egg
Predict the sign of change of
AH = -92.4KJ
13 Nz(g) + 3A2(g) ’ 2NHs(g)
formation of NH3?
What is the standard enthalpy of
Ans = 46.2 KJ/mol

two reaction are given below

The values of AH and AS for AS
AH
AS = +31 JIKmol
AH =10.5 % 103 Jimol

AS = 105 JIKmol
b AH =11.7 x 103 Jlmol

spontaneous or not at 298 K

Decide whether these reactions are

by carbon becomes
15 At what temperature does the reduction of lead oxide to lead

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 CLASS XI
spontaneous? PbO +C’ Pb(s) + Co(g)
THERMODYNAMICS
SANDiSH ARO
SIve tFor the reactlon AH and As at 25C are 408,4 KJimol and 190 JIKmol
respectively Ans 570.5K
16 Arrange the following in the order of Increasing entropy

a. 1 mol of H20(s) at 0oC and 1 atm

b. 1 mol of H2o(0) at 0oC and 1 atm
C. 1mol of H20() at 25"C and 1 atm
d. 1 mol of H20(0) at 25°C and 0.8 atm
e. 1mol of H20(v) at 100C and 1 atm

1|An exothermic reaction X’Yis spontaneous in the backwards direction. What is the
sign of AS for forward reaction
18 Comment on the thermodynamic stability of NO(g) given
½ Na(g) + % O(g) ’ NO A,H= 90KJ/mol
NO(g) + Oz(g) ’ NO2 AH =-74KJ/mol
19 What is the sign of AH for
a. Evaporation of liquid water b. Freezing of liquid water
20 S + O2’ S02 + 2x Kcal
SO2+ V.02 ’ SO, 4yKcal
What is the heat of formation of SO3
21 Predict the feasibility of the reaction, 2Hgo (s)> 2Hg (0) + 02 (g) at 298K

Given : AH = 91KJ/mol, 4S (Hg0) = 72 JIKmol

AS (Hg) = 774 JIKmol, AS (02) = 205 JIKmol
22 Sodium carbonate can be obtained by decomposition of sodium bicarbonate .Calculate
the temperature above which reaction. is feasible Given
NaHCO 3 Na z CO 3 CO 2 H20
Enthalpy of -947.7 -1130.9 -393.51 -241.82
formation
KJ/mol
Entropy Jimol 102.1 136 188.83 213.74
Ans 129.17 KJ/mol 334.37 Jlmol 386 K
23 The standard Gibbs-energy change for formation of ammonia by the Haber's process is
-33.2 KJlmol at 298 K. calculate a) Equilibrium constant for reaction b) Calculate
equilibrium constant for decomposition of ammon ia Ans : 6.6 x 10 5
24 Predictfeasibility of reaction 2A (g) +B(9) -2 D(s) Change in internal energy is -10.5
KJ and Change in entropy is - 44.1 JIK .Calculate gibbes free energy , predict feasibility
of reaction at 298-K
Ans : 12.9 KJ/nol ,0.1165 KJ/mol
or the reaction at 298 K, 2A+B’C change in enthalpy is 400 KJ mol and change in
25
entropy is 0.2 K-1J1mol, at what temnperature will the reaction become spontaneous
considering change in enthalpy and change in entropy to be constant over the
temperature range? [ans: 2000K]
and 1atm pressure
26 Calculate the equilibrium constant for the following reaction at 298K
NO(g) + ½02 (g) ’ NO2 (g)
= 90.4 kJ-mol and NO2 (g) =
Given the change at gibbs free energy at 298 K are NO(g) -70.0 J-1k 1mol,
reaction =
33.8 kJ-4mol, change in entropy at 298K for the
R=8.31 J1K^mol. [ans:1.85x 109]

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