CHEMICAL EQUILIBRIUM

COMPILED BY:
DR. SAYAN ROY CHOWDHURY

For more details, call: 7384905704 / 8961460392

 CHEMICAL EQUILIBRIUM
(Following material comprised of detailed theory, with outside questions and
discussion)

Compiled by

Dr Sayan Roy Chowdhury

Associates with Dept. of Chemical Technology, CU
Senior research associate
Author of International journals
https://www.researchgate.net/profile/Sayan_Roychowdhury
 Partial Molar Quantity
From the free energy change and from the law of thermodynamics we can write,G = f(T, P),
(For one component close system). For multicomponent system, the amount of various
substances are treated as variables as any other thermodynamic variables (viz. T and P). For
example Gibbs free energy of a system is not only a function of T and P, but also the amount of
each substance present in that system which can be denoted as
G = f(T, P, n1 , n2 , … … nk )
Where,n1 , n2 , … … nk represents the amount of each of the k components present in the system.
Suppose the system is composed of two components.
G = f(T, P, n1 , n2 )
∂G ∂G ∂G ∂G
dG = ( ) dT + ( ) dP + ( ) dn1 + ( ) dn
∂T P,n1,n2 ∂P T,n1 ,n2 ∂n1 T,P,n2 ∂n2 T,P,n1 2
∂G ∂G
In this equation,(∂n ) and (∂n ) are known as partial molar free quantities of
1 T,P,n2 2 T,P,n1
component 1 and 2.

Definition:The partial derivative of a thermodynamic function ‘X’ with respect to the amount of
component ‘i’ of a mixture when the temperature, pressure and the amounts of other
constituents are kept constant are known as partial molar quantities of ith component and
represented as,
𝛛𝐗
𝐗 𝐢,𝐩𝐦 = ( )
𝛛𝐧𝐢 𝐓,𝐏,𝐧 𝐣𝐬
𝐣≠𝐢

Physical significance of partial molar quantity

Xi,pm be the actual values of X per mole of ith species in a system of known composition, which
may or may not be equal to the molar values of X in the pure state. For only ideal system where
either there exists no interaction between the constituents (ideal gasses) or all the interaction
are of the same type (ideal solution) , then the two values are same (Partial molar value and
molar value).
In non ideal solution because of interaction between the constituents, the molar value of Xi∗ get
modified to a new value Xi,pm . Since the extent of interactions depends upon the relative
amounts of components, it is obvious that the modified value of X may not be the same of all
composition.
Hence its value will also depend upon the composition of the solution. Thus, although the
partial molar quantity of individual, their values are not only dependent on the nature of the
particular substance but also on the nature and amounts of other components present in the
system.
Q. The partial molar volume of acetone and chloroform in a mixture in which the mole
fraction of acetone is 0.53 are 74.17 cc/mole and 80.24 cc/mole. What is the density of
the solution? What will be the volume of the solution weighing 1 kg?
Let us consider a solution containing 0.53 mole of acetone and 0.47 mole of chloroform. The
volume of the solution
V = n1 V1,pm + n2 V2,pm
cc cc
V = (0.53 mole) (74.17 ) + (0.47 mole) (80.24 ) = 77.02 cc
mole mole
The mass of the solution will be
m = n1 M1 + n2 M2
gm gm
m = (0.53 mole) (58 ) + (0.47 mole) (119.5 ) = 86.91 gm
mole mole
m 86.91 gm gm
The density of the solution will be, ρ = = = 1.128
V 77.02 cc cc
77.02 cc
The volume of 1 kg solution will be = 1000gm × 86.91 gm = 886.2 cc

Define chemical potential

It is the molar quantities of free energy. More precisely it can be written that partial molar free
energy Gi,pm . The chemical potential of any constituent ‘i’ can be denoted, derivation of the free
energy with the amount of ith component keeping the temperature, pressure and the amount of
other constituents remains unaltered.
∂G
μi = ( )
∂ni T,P,n
js
j≠i

Because of it is a molar quantity, it is molar intensive property.

Expression of 𝐝𝐄, 𝐝𝐇, 𝐝𝐀 𝐚𝐧𝐝 𝐝𝐆 for multicomponent system

If a system contains a total of ‘k’ components then

G = f(T, P, n1 , n2 , … … nk )
k
∂G ∂G ∂G
dG = ( ) dT + ( ) dP + ∑ ( ) dni
∂T P,njs ∂P T,njs ∂ni T,P,n
i=1 js
j≠i
Then the equation can be written as,
k
∂G ∂G
dG = ( ) dT + ( ) dP + ∑ μi dni
∂T P,njs ∂P T,njs
i=1
k

dG = −SdT + VdP + ∑ μi dni … … … . . (1)

i=1
We know that G = H − TSandA = E − TS, so, G = E + PV − TS = A + PV
Hence G = A + PV, or, dG = dA + PdV + VdP … … . . (ii)
Putting the values of (i) in equation (ii)
k

−SdT + VdP + ∑ μi dni = dA + PdV + VdP

i=1
k

dA = −SdT − PdV + ∑ μi dni … … … . . (3)

i=1
Again we can write that G = H − TS, or, dG = dH − TdS − SdT
k

−SdT + VdP + ∑ μi dni = dH − TdS − SdT

i=1
k

dH = TdS + VdP + ∑ μi dni … … … (4)

i=1
Helmholtz free energy can be written as, A = E − TS
or, dA = dE − TdS − SdT
So, from equation (3) we can write,
k

−SdT − PdV + ∑ μi dni = dE − TdS − SdT

i=1
k

dE = TdS − PdV + ∑ μi dni … … . (5)

i=1
Hence, from equation (1), (3), (4) and (5)

𝛛𝐆 𝛛𝐄 𝛛𝐀 𝛛𝐇
𝛍𝐢 = ( ) =( ) =( ) =( )
𝛛𝐧𝐢 𝐓,𝐏,𝐧 𝐣𝐬 𝛛𝐧𝐢 𝐒,𝐕,𝐧 𝐣𝐬 𝛛𝐧𝐢 𝐓,𝐕,𝐧 𝐣𝐬 𝛛𝐧𝐢 𝐒,𝐏,𝐧 𝐣𝐬
𝐣≠𝐢 𝐣≠𝐢 𝐣≠𝐢 𝐣≠𝐢

Express the function V, E, H, S, A and G by the definition of partial molar quantities

𝛛𝐕 𝛛𝐄 𝛛𝐆
𝐕𝐢,𝐩𝐦 = ( ) 𝐄𝐢,𝐩𝐦 = ( ) 𝐆𝐢,𝐩𝐦 = ( )
𝛛𝐧𝐢 𝐓,𝐏,𝐧 𝐣𝐬 𝛛𝐧𝐢 𝐓,𝐏,𝐧 𝐣𝐬 𝛛𝐧𝐢 𝐓,𝐏,𝐧 𝐣𝐬
𝐣≠𝐢 𝐣≠𝐢 𝐣≠𝐢
𝛛𝐀 𝛛𝐇 𝛛𝐒
𝐀 𝐢,𝐩𝐦 =( ) 𝐇𝐢,𝐩𝐦 =( ) 𝐒𝐢,𝐩𝐦 =( )
𝛛𝐧𝐢 𝐓,𝐏,𝐧 𝐣𝐬 𝛛𝐧𝐢 𝐓,𝐏,𝐧 𝐣𝐬 𝛛𝐧𝐢 𝐓,𝐏,𝐧 𝐣𝐬
𝐣≠𝐢 𝐣≠𝐢 𝐣≠𝐢

Define chemical potential

If a small amount of substance ‘i’, dni moles, is added to a system keeping temperature and
pressure and all the other mole number constant and maintaining the virtual equilibrium, then
the increase in Gibbs free energy per mole of the substance is called the chemical potential of
that substance,
 𝛛𝐆
𝛍𝐢 = ( )
𝛛𝐧𝐢 𝐓,𝐏,𝐧 𝐣𝐬
𝐣≠𝐢

Chemical potential is an extensive property---Justify and criticize

Chemical potential can be represented by the change of free energy per change of mole number
keeping all the other factor constant. Hence free energy is an extensive property. So the change
of free energy is also an extensive property. Amount of each substance is an extensive property.
So the amount of change of substance is also an extensive property. The ratio of two extensive
properties is known as intensive property.

Why 𝛍𝐢 is known as chemical potential?

Matter flows spontaneously from a region of high chemical potential to low chemical potential
such as electric current flows spontaneously from high electric potential to low electric
potential or mass flow spontaneously from high gravitational potential to low gravitational
potential. Thus the substance ‘i’ flows spontaneously from high μi to low μi , which continues
until the value of μi uniform throughout the system to maintain equilibrium. That is why to
maintain the equilibrium to system, the property μi is called the chemical potential of substance
i.

Q. Prove that 𝐇𝐢,𝐩𝐦 = 𝐄𝐢,𝐩𝐦 + 𝐏𝐕𝐢,𝐩𝐦

From the definition we can write, H = E + PV
Differentiating the equation with respect to ith component keeping T, P and the amount of all
other constituents remain constant
∂H ∂E ∂V
( ) =( ) +P( )
∂ni T,P,n ∂ni T,P,n ∂ni T,P,n
js js js
j≠i j≠i j≠i
or, Hi,pm = Ei,pm + PVi,pm
Similar prove are done as follows
G = H − TS A = E − TS
∂G ∂H ∂S ∂A ∂E ∂S
( ) =( ) − T( ) ( ) =( ) − T( )
∂ni T,P,n ∂ni T,P,n ∂ni T,P,n ∂ni T,P,n ∂ni T,P,n ∂ni T,P,n
js js js js js js
j≠i j≠i j≠i j≠i j≠i j≠i
or, Gi,pm = Hi,pm − TSi,pm or, Ai,pm = Ei,pm − TSi,pm

Q. With increasing the temperature at constant P and all the other constituents remains
constant, chemical potential of the substance decreases-----justify or criticize or prove
that
𝛛𝛍𝐢
( ) = −𝐒𝐢,𝐩𝐦
𝛛𝐓 𝐏,𝐧𝐣𝐬
From the definition of chemical potential, we can write that,
 μi = Gi,pm
Differentiating with respect to T, keeping P and njs constant

∂μi ∂Gi,pm ∂ ∂G
( ) =( ) ={ ( ) }
∂T P,njs ∂T P,n ∂T ∂ni T,P,n
js js
j≠i P,njs
Since G is a state function,
∂μi ∂ ∂G ∂
( ) ={ ( ) } ={ (−S)} = −Si,pm
∂T P,njs ∂ni ∂T P,njs ∂ni T,P,n
T,P,n js js
j≠i j≠i

Q. Prove that
𝛛𝛍𝐢
( ) = 𝐕𝐢,𝐩𝐦
𝛛𝐏 𝐓,𝐧𝐣𝐬
From the definition of chemical potential, we can write that,
μi = Gi,pm
Differentiating with respect to P, keeping T and njs constant

∂μi ∂Gi,pm ∂ ∂G
( ) =( ) ={ ( ) }
∂P T,njs ∂P T,n ∂P ∂ni T,P,n
js js
j≠i T,njs
Since G is a state function,
∂μi ∂ ∂G ∂
( ) ={ ( ) } ={ (V)} = Vi,pm
∂P T,njs ∂ni ∂P T,njs ∂ni T,P,n
T,P,n js js
j≠i j≠i

Q. Prove that
𝛛 ∆𝛍𝐢 ∆𝐇𝐢,𝐩𝐦
[ ( )] =−
𝛛𝐓 𝐓 𝐏,𝐧𝐣𝐬 𝐓𝟐
We can write from concept of partial molar quantities,
μi = Gi,pm = Hi,pm − TSi,pm
For finite change in process we can write that,
∆μi = ∆Gi,pm = ∆Hi,pm − T∆Si,pm … … … (1)
We can write that,
∂ ∆μi ∆μi 1 ∂∆μi
[ ( )] =− 2 + ( )
∂T T P,njs T T ∂T P,njs

Putting the value from equation (1)

 ∂ ∆μi (∆Hi,pm − T∆Si,pm ) 1 ∂∆μi
[ ( )] =− + ( )
∂T T P,njs T2 T ∂T P,njs

∂ ∆μi ∆Hi,pm ∆Si,pm ∆Si,pm

[ ( )] =− + −
∂T T P,njs T2 T T

∂ ∆μi ∆Hi,pm
[ ( )] =−
∂T T P,njs T2

Q. Write a short note on escaping tendency

Suppose a substance is present in different phase αand β. So the chemical potential of that
substance is same, if the substance be in equilibrium. We can write that, μα = μβ
If dn be the amount of substance transfer from αto β. So the two equations becomes,
dGα = μα (−dn)and, dG β = μβ (dn)
So the total change in free energy of the system, dG = dGα + dG β = (μβ − μα )dn
Case-1, If μα > μβ , dn = (+)ve, dG = (−)ve Then the above transfer of substance from α to β
occur spontaneously.

Case-2, If μα < μβ , dn = (+)ve, dG = (+)ve Then the above transfer of substance from α toβ,
become non spontaneous.
thus in the 1st case, the substance spontaneously flow from higher chemical potential α to lower
chemical potential β, until and unless dG becomes zero to maintain an equilibrium, which is
known as escaping tendency.

Theory of Chemical Potential

Relation between formal and pure chemical potential

For multi-component ideal gas mixture we can write

𝛛𝛍𝐢
( ) = 𝐕𝐢,𝐩𝐦
𝛛𝐏 𝐓,𝐧𝐣𝐬
Here Vi,pm is the partial molar volume of the ith component or the volume of that particular ith
component within the total volume of the system
𝛛𝛍𝐢 𝐑𝐓
( ) =
𝛛𝐏 𝐓,𝐧𝐣𝐬 𝐏𝐢
Pi is the pressure exerted by the ith component of the mixture
𝛍𝐢𝟐 𝐏𝐢𝟐
𝐝𝐏
∫ 𝐝𝛍𝐢 = 𝐑𝐓 ∫
𝐏𝐢
𝛍𝐢𝟏 𝐏𝐢𝟏
 𝐏𝐢𝟐
𝛍𝐢𝟐 (𝐓, 𝐏𝐢𝟐 ) − 𝛍𝐢𝟏 (𝐓, 𝐏𝐢𝟏 ) = 𝐑𝐓 𝐥𝐧… . . (1)
𝐏𝐢𝟏
The above relation reveals the change in chemical potential at a constant temperature due to
change of pressure from state 1 (Pi1) to state 2 (Pi1)
When ith component present alone then it will exert its pure vapor pressure (denoted by Pi∗ )
which is equal to the total pressure of the container. Then the chemical potential of that state is
known as pure chemical potential 𝛍∗𝐢

𝛍𝐢𝟏 (𝐓, 𝐏𝐢𝟏 ) = 𝛍∗𝐢 (𝐓, 𝐏𝐢∗ ) … . (𝐚)

When ith component present in a mixture state along with other component then it will exert
its partial vapor pressure (denoted by 𝐏𝐢 ) which is equal to the pressure exerted by it only
within the total pressure. Then the chemical potential of that state is known as formal chemical
potential 𝛍𝐢 (𝐓, 𝐏𝐢 )

𝛍𝐢𝟐 (𝐓, 𝐏𝐢𝟐 ) = 𝛍𝐢 (𝐓, 𝐏𝐢 ) … (b)

Putting the concept (a) and (b) in equation (1) the following result is obtain
𝐏𝐢
𝛍𝐢 (𝐓, 𝐏𝐢 ) − 𝛍∗𝐢 (𝐓, 𝐏𝐢∗ ) = 𝐑𝐓 𝐥𝐧 ∗
𝐏𝐢

The above relation relates pure chemical potential with formal chemical potential

Relation between standard and pure chemical potential

State 1, Pi1 = 1 atm = Po
If the ith component will exert 1 atm then the state 1 chemical potential is known as standard
chemical potential (denoted by μ0i (T)) which is a function of temperature.
𝛍𝐢𝟏 (𝐓, 𝐏𝐢𝟏 ) = 𝛍𝟎𝐢 (𝐓)
State 2, Pi2 = pure vapor pressure = Pi∗
If the state 2 represent the pure form of i that give pure vapor pressure Pi∗ and chemical
potential of state 2 represent the pure chemical potential μ∗i (T, Pi∗ )
𝛍𝐢𝟐 (𝐓, 𝐏𝐢𝟐 ) = 𝛍∗𝐢 (𝐓, 𝐏𝐢∗ )
Then using the above concept in equation (1)
𝐏𝐢∗
𝛍∗𝐢 (𝐓, 𝐏𝐢∗ ) − 𝛍𝟎𝐢 (𝐓) = 𝐑𝐓 𝐥𝐧 … … (𝟐)
𝐏𝐨
We get a relation that relates pure chemical potential with standard chemical potential

Relation between standard and formal chemical potential

State 1, 𝐏𝐢𝟏 = 𝟏 𝐚𝐭𝐦 = 𝐏𝐨
If the ith component will exert 1 atm then the state 1 chemical potential is known as standard
chemical potential (denoted by μ0i (T)) which is a function of temperature.

𝛍𝐢𝟏 (𝐓, 𝐏𝐢𝟏 ) = 𝛍𝟎𝐢 (𝐓)

If the state 2 represent the mix form of i that gives partial vapor pressure Pi and then the
chemical potential of state 2 represent the formal chemical potential μi (T, Pi )
State 2, Pi2 = partial vapor pressure = Pi
μi2 (T, Pi2 ) = μi (T, Pi )
Then using the above concept in equation (1)
𝐏𝐢
𝛍𝐢 (𝐓, 𝐏𝐢 ) − 𝛍𝟎𝐢 (𝐓) = 𝐑𝐓 𝐥𝐧 … … (𝟑)
𝐏𝐨
We get a relation that relates formal chemical potential with standard chemical potential
Subtracting equation (2) from equation (3) we get equation (1)
which is the relation of formal chemical with pure chemical potential

Pure chem. Pot. Is lower than formal chem. Pot.

When ith component present alone then it will exert its pure vapor pressure (denoted by Pi∗ )
which is equal to the total pressure of the container. Then the chemical potential of that state is
known as pure chemical potential μ∗i

From the relation of μ∗i with standard chemical 𝛍𝟎𝐢

𝐏𝐢∗
𝛍∗𝐢 (𝐓, 𝐏𝐢∗ ) = 𝛍𝟎𝐢 (𝐓) + 𝐑𝐓 𝐥𝐧 … . . (𝐀)
𝐏𝐨
When ith component present in the mixture state then it will exert partial pressure which is
equal to the mole fraction of that component in vapor phase multiplied by total pressure at that
stage (which is equal to the pure vapor pressure of ith component when i present alone)

𝐏𝐢 = 𝐲𝐢𝐯 𝐏𝐓 = 𝐲𝐢𝐯 𝐏𝐢∗

From the relation of formal chemical potential with standard one

𝐏𝐢
𝛍𝐢 (𝐓, 𝐏𝐢 ) − 𝛍𝟎𝐢 (𝐓) = 𝐑𝐓 𝐥𝐧
𝐏𝐨
Putting the value of Pi in the above equation we get
𝐲𝐢𝐯 𝐏𝐢∗
𝛍𝐢 (𝐓, 𝐏𝐢 ) − 𝛍𝟎𝐢 (𝐓) = 𝐑𝐓 𝐥𝐧
𝐏𝐨
∗
𝐏𝐢
𝛍𝐢 (𝐓, 𝐏𝐢 ) = 𝛍𝟎𝐢 (𝐓) + 𝐑𝐓 𝐥𝐧 + 𝐑𝐓 𝐥𝐧 𝐲𝐢𝐯
𝐏𝐨
With the help of equation (A)
𝛍𝐢 (𝐓, 𝐏𝐢 ) = 𝛍∗𝐢 (𝐓, 𝐏𝐢∗ ) + 𝐑𝐓 𝐥𝐧 𝐲𝐢𝐯
As yiv is less than 1, ln yiv = (−)ve, hence it readily observed that μi (T, Pi ) < μ∗i (T, Pi∗ ), so pure
chemical potential is always higher than formal chemical potential. According to the escaping
tendency ith component spontaneously move from pure state to formal state.

Gibbs Duhem equation

Suppose a multi-component mixture (1, 2, 3, … i, …) with mole n1 , n2 , n3 …. having a partial
molar free energies G1,pm , G2,pm , G3,pm …. And so on. Then the total free energy of the system can
be written as
𝐆 = 𝐧𝟏 𝐆𝟏,𝐩𝐦 + 𝐧𝟐 𝐆𝟐,𝐩𝐦 + 𝐧𝟑 𝐆𝟑,𝐩𝐦 + ⋯
𝐤 𝐤

𝐆 = ∑ 𝐧𝐢 𝐆𝐢,𝐩𝐦 = ∑ 𝐧𝐢 𝛍𝐢
𝐢=𝟏 𝐢=𝟏
Differentiating both sides of the equation
𝐤 𝐤 𝐤 𝐤

𝐝𝐆 = 𝐝 ∑ 𝐧𝐢 𝛍𝐢 = ∑ 𝐝(𝐧𝐢 𝛍𝐢 ) = ∑ 𝐧𝐢 𝐝𝛍𝐢 + ∑ 𝛍𝐢 𝐝𝐧𝐢 … … . (𝟏𝐚)

𝐢=𝟏 𝐢=𝟏 𝐢=𝟏 𝐢=𝟏
From the multi-component system
 𝐤

𝐝𝐆 = −𝐒𝐝𝐓 + 𝐕𝐝𝐏 + ∑ 𝛍𝐢 𝐝𝐧𝐢 … … … . (𝟏𝐛)

𝐢=𝟏
Equating (1a) with (1b)
𝐤

∑ 𝐧𝐢 𝐝𝛍𝐢 = −𝐒𝐝𝐓 + 𝐕𝐝𝐏

𝐢=𝟏
At constant T and P
𝐤

∑ 𝐧𝐢 𝐝𝛍𝐢 = 𝟎
𝐢=𝟏

The above equation is known as Gibbs Duhem equation

If we consider a binary component system (1 and 2) then we can write that

𝐧𝟐
𝐧𝟏 𝐝𝛍𝟏 + 𝐧𝟐 𝐝𝛍𝟐 = 𝟎 𝐝𝛍𝟏 = − 𝐝𝛍𝟐
𝐧𝟏
Here both n1 and n2 are positive quantity, So increment of chemical potential of 2 will result a
decrement of chemical potential of 1 and vice versa.

Suppose a multi-component mixture (1, 2, 3, … i, …) with mole n1 , n2 , n3 …. having a partial

molar volume V1,pm , V2,pm , V3,pm …. And so on. Then the total volume of the system can be
written as
𝐕 = 𝐧𝟏 𝐕𝟏,𝐩𝐦 + 𝐧𝟐 𝐕𝟐,𝐩𝐦 + 𝐧𝟑 𝐕𝟑,𝐩𝐦 + ⋯
𝐤

𝐕 = ∑ 𝐧𝐢 𝐕𝐢,𝐩𝐦
𝐢=𝟏
Differentiating both sides of the equation
𝐤 𝐤 𝐤 𝐤

𝐝𝐕 = 𝐝 ∑ 𝐧𝐢 𝐕𝐢,𝐩𝐦 = ∑ 𝐝(𝐧𝐢 𝐕𝐢,𝐩𝐦 ) = ∑ 𝐧𝐢 𝐝𝐕𝐢,𝐩𝐦 + ∑ 𝐕𝐢,𝐩𝐦 𝐝𝐧𝐢 … . (𝟐𝐚)

𝐢=𝟏 𝐢=𝟏 𝐢=𝟏 𝐢=𝟏
Now we can written as
𝐕 = 𝐟(𝐓, 𝐏, 𝐧𝟏 , 𝐧𝟐 , … . . 𝐧𝐤 )
Then
𝛛𝐕 𝛛𝐕 𝛛𝐕 𝛛𝐕
𝐝𝐕 = ( ) 𝐝𝐓 + ( ) 𝐝𝐏 + ( )𝐓,𝐏,𝐧 𝐝𝐧𝟏 + ( ) 𝐝𝐧 + ⋯
𝛛𝐓 𝐏,𝐧𝐣𝐬 𝛛𝐏 𝐓,𝐧𝐣𝐬 𝛛𝐧𝟏 𝐣𝐬 𝛛𝐧𝟐 𝐓,𝐏,𝐧𝐣𝐬 𝟐
𝐣≠𝟏 𝐣≠𝟐

𝐤
𝛛𝐕 𝛛𝐕 𝛛𝐕
𝐝𝐕 = ( ) 𝐝𝐓 + ( ) 𝐝𝐏 + ∑ ( )𝐓,𝐏,𝐧 𝐝𝐧𝐢
𝛛𝐓 𝐏,𝐧𝐣𝐬 𝛛𝐏 𝐓,𝐧𝐣𝐬 𝛛𝐧𝐢 𝐣𝐬
𝐢=𝟏 𝐣≠𝐢
 𝐤
𝛛𝐕 𝛛𝐕
𝐝𝐕 = ( ) 𝐝𝐓 + ( ) 𝐝𝐏 + ∑ 𝐕𝐢,𝐩𝐦 𝐝𝐧𝐢 … … . (𝟐𝐛)
𝛛𝐓 𝐏,𝐧𝐣𝐬 𝛛𝐏 𝐓,𝐧𝐣𝐬
𝐢=𝟏

Equating (2a) with (2b)

k

dV = ∑ 𝐕𝐢,𝐩𝐦 d𝐧𝐢
i=1

∑ 𝐧𝐢 𝐝𝐕𝐢,𝐩𝐦 = 𝟎
𝐢=𝟏

If we consider a binary component system (1 and 2) then we can write that

n2
n1 dV1,pm + n2 dV2,pm = 0 dV1,pm = − dV2,pm
n1
Here both 𝐧𝟏 and 𝐧𝟐 are positive quantity, So increment of molar volume of 2 will result a
decrement of molar volume of 1 and vice versa.

Isothermal Isobaric mixing of ideal gas

Let us assume k numbers of components (ideal gasses) are taken in a different compartment by
different amount at same temperature and pressure. After some time the compartment barriers
are to be taken out, as a result k number of components are mixed together. The process is
conducted in such a way that the temperature and pressure of the system remains constant.

Before mixing, each gas will exert a pressure P which is the pure vapor pressure of that gas.
Pi∗ = P
Then the chemical potential of each present in each compartment is the pure chemical potential
which relates to standard chemical potential as
𝐏
𝛍∗𝐢 (𝐓, 𝐏) = 𝛍𝟎𝐢 (𝐓) + 𝐑𝐓 𝐥𝐧 … (𝟏𝐜)
𝐏𝟎
𝐤

𝐆𝐢𝐧𝐢 = ∑ 𝐧𝐢 𝛍∗𝐢 (𝐓, 𝐏) … . (𝟏𝐝)

𝐢=𝟏

After mixing, the mixing carried out in such a way that the total pressure of the container is
equal to the pressure exerted by each component before mixing. Now each component will
exhibit a pressure (Pi , partial pressure) lower than the previous pressure P
According to Daltons law
𝐏𝐢 = 𝐲𝐢𝐯 𝐏
Now the chemical potential of each component after mixing is denoted by formal chemical
potential which relates to partial pressure as
𝐏𝐢
𝛍′𝐢 (𝐓, 𝐏𝐢 ) = 𝛍𝟎𝐢 (𝐓) + 𝐑𝐓 𝐥𝐧
𝐏𝟎
Now putting the value of Pi from above
𝐲𝐢𝐯 𝐏 𝐏
𝛍′𝐢 (𝐓, 𝐏𝐢 ) = 𝛍𝟎𝐢 (𝐓) + 𝐑𝐓 𝐥𝐧 𝐨𝐫, 𝛍′𝐢 (𝐓, 𝐏𝐢 ) = 𝛍𝟎𝐢 (𝐓) + 𝐑𝐓 𝐥𝐧 + 𝐑𝐓 𝐥𝐧 𝐲𝐢𝐯
𝐏𝟎 𝐏𝟎

Now from equation (1c)

𝛍′𝐢 (𝐓, 𝐏𝐢 ) = μ∗i (T, P) + 𝐑𝐓 𝐥𝐧 𝐲𝐢𝐯

𝐤 𝐤 𝐤 𝐤

𝐆𝐟𝐢𝐧𝐚𝐥 = ∑ 𝐧𝐢 𝛍′𝐢 (𝐓, 𝐏𝐢 ) = ∑ 𝐧𝐢 {μ∗i (T, P) + 𝐑𝐓 𝐥𝐧 𝐲𝐢𝐯 } = ∑ 𝐧𝐢 μ∗i (T, P) + ∑ 𝐧𝐢 𝐑𝐓 𝐥𝐧 𝐲𝐢𝐯

𝐢=𝟏 𝐢=𝟏 𝐢=𝟏 𝐢=𝟏

Now from equation (1d)

𝐤

𝐆𝐟𝐢𝐧𝐚𝐥 = 𝐆𝐢𝐧𝐢 + 𝐑𝐓 ∑ 𝐧𝐢 𝐥𝐧 𝐲𝐢𝐯

𝐢=𝟏

∆𝐆𝐦𝐢𝐱 = (𝐆𝐟𝐢𝐧𝐚𝐥 − 𝐆𝐢𝐧𝐢 ) = 𝐑𝐓 ∑ 𝐧𝐢 𝐥𝐧 𝐲𝐢𝐯

𝐢=𝟏

𝐤 𝐤
∆𝐆𝐦𝐢𝐱 𝐑𝐓 𝐧𝐢
̃𝐦𝐢𝐱
∆𝐆 = = ∑ 𝐧𝐢 𝐥𝐧 𝐲𝐢𝐯 = 𝐑𝐓 ∑ 𝐥𝐧 𝐲𝐢𝐯
𝐧𝐭𝐨𝐭𝐚𝐥 𝐧𝐭𝐨𝐭𝐚𝐥 𝐧𝐭𝐨𝐭𝐚𝐥
𝐢=𝟏 𝐢=𝟏

𝐤
̃𝐦𝐢𝐱 = 𝐑𝐓 ∑ 𝐲𝐢𝐯 𝐥𝐧 𝐲𝐢𝐯
∆𝐆
𝐢=𝟏

̃mix always occur spontaneously.

As yiv is less than 1, ln yiv = (−)ve, so ∆G

Considering fundamental equation in case of finite change of mixing

∂∆𝐆̃𝐦𝐢𝐱
( ) = −∆𝐒̃𝐦𝐢𝐱
∂T P
𝐤

∆𝐒̃𝐦𝐢𝐱 = −𝐑 ∑ 𝐲𝐢𝐯 𝐥𝐧 𝐲𝐢𝐯

𝐢=𝟏
From Gibbs Helmholtz equation
 ̃𝐦𝐢𝐱 = ∆𝐇
∆𝐆 ̃ 𝐦𝐢𝐱 − 𝐓∆𝐒̃𝐦𝐢𝐱
∆𝐇̃ 𝐦𝐢𝐱 = 𝟎

Binary mixing of ideal gas isothermally and isobarically

∆𝐆̃𝐦𝐢𝐱 = 𝐑𝐓(𝐲𝟏 𝐥𝐧 𝐲𝟏 + 𝐲𝟐 𝐥𝐧 𝐲𝟐 )
For binary system, 𝐲𝟏 + 𝐲𝟐 = 𝟏 or 𝐲𝟐 = 𝟏 − 𝐲𝟏
Putting the value of 𝐲𝟐 in the above equation
∆𝐆̃𝐦𝐢𝐱 = 𝐑𝐓{𝐲𝟏 𝐥𝐧 𝐲𝟏 + (𝟏 − 𝐲𝟏 ) 𝐥𝐧(𝟏 − 𝐲𝟏 )}
In order to get minimum
𝐝∆𝐆̃𝐦𝐢𝐱 𝐲𝟏 (𝟏 − 𝐲𝟏 ) 𝐲𝟏
= 𝐑𝐓 {𝐥𝐧 𝐲𝟏 + + 𝐥𝐧(𝟏 − 𝐲𝟏 ) − } = 𝐑𝐓 𝐥𝐧 =𝟎
𝐝𝐲𝟏 𝐲𝟏 (𝟏 − 𝐲𝟏 ) (𝟏 − 𝐲𝟏 )
𝐲𝟏 𝐲𝟏
𝐥𝐧 = 𝐥𝐧 𝟏 𝐨𝐫, = 𝟏 𝐨𝐫, 𝐲𝟏 = 𝟏⁄𝟐
(𝟏 − 𝐲𝟏 ) (𝟏 − 𝐲𝟏 )
𝐲𝟐 = 𝟏 − 𝟏⁄𝟐 = 𝟏⁄𝟐
Hence the magnitude of minimum value of ∆𝐆 ̃𝐦𝐢𝐱
̃𝐦𝐢𝐱 = 𝐑𝐓{𝟏⁄ 𝐥𝐧 𝟏⁄ + (𝟏 − 𝟏⁄ ) 𝐥𝐧(𝟏 − 𝟏⁄ )} = −𝐑𝐓 𝐥𝐧 𝟐
∆𝐆 𝟐 𝟐 𝟐 𝟐

∆𝐒̃𝐦𝐢𝐱 = −𝐑(𝟏⁄𝟐 𝐥𝐧 𝟏⁄𝟐 + 𝟏⁄𝟐 𝐥𝐧 𝟏⁄𝟐) = 𝐑 𝐥𝐧 𝟐

 Chemical Reaction Thermodynamics

Suppose a chemical reaction be represented as

𝐚𝐀 + 𝐛𝐁 = 𝐜𝐂 + 𝐝𝐃
Where,a, b are reactant stoichiometry and c, d are product stoichiometry. A, Bare the reactants and C, D are
product. Product is always (+) ve and reactant is always (−) ve.
So, the equation can be written in form
𝐜𝐂 + 𝐝𝐃 − 𝐚𝐀 − 𝐛𝐁 = 𝟎 𝐨𝐫, 𝐜𝐂 + 𝐝𝐃 + (−𝐚)𝐀 + (−𝐛)𝐁 = 𝟎
So any reaction can be represented as
∑ 𝛎𝐁 𝐁 = 𝟎
𝐁
where B represents the constituents of the reaction and νB represent the stoichiometric co-efficient.
the progress of any reaction can be represented with respect to any constituents,
𝐧(𝐁)−𝐧𝟎 (𝐁)
n(B) = n0 (B) + νB ξ or, = (𝛏 − 𝟎)
𝛎𝐁
𝐝𝐧𝐁
In differential form = 𝛎𝐁 where 𝛏 be the extent of the reaction.
𝐝𝛏
General form of a chemical reaction
A chemical reaction can be represented by the form
│ν1 │A1 + │ν2 │A2 → ν3 A3 + ν4 A4
if the reaction started with n0 moles of both A1 and A2 . After some time t we can write the
amounts of different constituents such as-
nt (A1 ) = n0 (A1 ) + │ν1 │ξ nt (A1 ) = n0 (A1 ) − ν1 ξ
nt (A2 ) = n0 (A2 ) + │ν2 │ξ nt (A2 ) = n0 (A2 ) − ν2 ξ
nt (A3 ) = ν3 ξ nt (A4 ) = ν4 ξ

Define reaction potential. How can a reaction be predicted towards its nature from chemical
potentials

The change in free energy function of a reaction (open system, multicomponent) due to
variation of temperature and pressure we can write,
𝐝𝐆 = −𝐒𝐝𝐓 + 𝐕𝐝𝐏 + ∑ 𝛍𝐁 𝐝𝐧𝐁 (𝟏)
𝐁
From the definition of progressment of the reaction
𝐝𝐧𝐁
= 𝛎𝐁 (2)
𝐝𝛏
Putting (2) in equation (1)
𝐝𝐆 = −𝐒𝐝𝐓 + 𝐕𝐝𝐏 + ∑ 𝛍𝐁 𝛎𝐁 𝐝𝛏 (3)
𝐁
 where∑𝐁(𝛍𝐁 𝛎𝐁 ) is called reaction potential which is represented as,
̃ = ∑(𝛍𝐁 𝛎𝐁 )
∆𝐫 𝐆
𝐁
Substituting in equation (3)
̃ dξ
dG = −SdT + VdP + ∆r G

𝛛𝐆
( 𝛛𝛏 ) ̃
= ∆𝐫 𝐆
𝐓,𝐏
i.e., the reaction potential is equal to the rate of change of total free energy with the extent of
reaction at constant temperature and pressure. From this equation we can write.
𝐝𝐆 = ∆𝐫 𝐆̃𝐝𝛏 at constant temperature and pressure
𝐂𝐚𝐬𝐞 - I: 𝐝𝐆 = ∆𝐫 𝐆̃𝐝𝛏 < 0 the reaction is spontaneous
𝐂𝐚𝐬𝐞 - II: 𝐝𝐆 = ∆𝐫 𝐆̃𝐝𝛏 > 0 the reaction is nonspontaneous
𝐂𝐚𝐬𝐞 - III: 𝐝𝐆 = ∆𝐫 𝐆 ̃𝐝𝛏 = 𝟎 the reaction at its equilibrium
We can write dG = ∆r G ̃dξ in case of forward reaction dξ = +ve
𝐂𝐚𝐬𝐞 - I: in case of spontaneous reaction, dG < 0 or, ∆r G ̃<0
A generalized chemical reaction,
𝛎𝟏 𝐀 𝟏 + 𝛎𝟐 𝐀 𝟐 → 𝛎 𝟑 𝐀 𝟑 + 𝛎𝟒 𝐀 𝟒
̃ = (𝛎𝟑 𝛍𝟑 + 𝛎𝟒 𝛍𝟒 ) − (|𝛎𝟏 |𝛍𝟏 + |𝛎𝟐 |𝛍𝟐 )
∆𝐫 𝐆
Hence,
(|𝛎𝟏 |𝛍𝟏 + |𝛎𝟐 |𝛍𝟐 ) > (𝛎𝟑 𝛍𝟑 + 𝛎𝟒 𝛍𝟒 )
Case-II: When ∆r G ̃ > 0, the reaction is nonspontaneous in the forward direction, in fact here
the backward reaction is spontaneous, so the product will be converted to the reactant.
(|𝛎𝟏 |𝛍𝟏 + |𝛎𝟐 |𝛍𝟐 ) < (𝛎𝟑 𝛍𝟑 + 𝛎𝟒 𝛍𝟒 )
Case-III: When ∆r G ̃ > 0, dG = 0, so the reaction will be at equilibrium
(|𝛎𝟏 |𝛍𝟏 + |𝛎𝟐 |𝛍𝟐 ) = (𝛎𝟑 𝛍𝟑 + 𝛎𝟒 𝛍𝟒 )

Let is consider a general equation

𝐚𝐀 + 𝐛𝐁 ⇌ 𝐦𝐌 + 𝐧𝐍
 ̃ = (𝐦𝛍𝐌 + 𝐧𝛍𝐍 ) − (𝐚𝛍𝐀 + 𝐛𝛍𝐁 )
∆𝐫 𝐆
 𝐜𝟎 𝐑𝐓 ∆𝛎𝐠
𝐐𝐏 = 𝐐𝐂 (
)
𝐏𝐨
𝐒𝐢𝐦𝐢𝐥𝐚𝐫𝐥𝐲 using Daltons law the relation between 𝐐𝐏 𝐚𝐧𝐝 𝐐𝐱 (follow class video)
𝐏 ∆𝛎𝐠
𝐐𝐏 = 𝐐𝐱 ( )
𝐏𝐨

𝐀𝐭 𝐞𝐪𝐮𝐢𝐥𝐢𝐛𝐫𝐢𝐮𝐦

𝐏 𝐦 𝐏 𝐧 𝐏𝐁 𝛎𝐁
( 𝐏𝐌 ) ( 𝐏𝐍 ) ∏𝐁,𝐩𝐝𝐭 (
𝐨 𝐞 𝐨 𝐞 𝐏𝐨 )𝐞
(𝐐𝐏 )𝐞 = = = 𝐊𝐏
𝐏 𝐚
𝐏𝐁 𝐛 𝐏𝐁 𝛎𝐁
( 𝐏𝐀 ) ( 𝐏 ) ∏𝐁,𝐫𝐞𝐚𝐜𝐭 ( )
𝐨 𝐞 𝐨 𝐞 𝐏𝐨 𝐞
𝐜 𝐦 𝐜 𝐧 𝐜 𝛎𝐁
( 𝐜𝐌 ) ( 𝐜𝐍 ) ∏𝐁,𝐩𝐝𝐭 ( 𝐁 )
𝐨 𝐞 𝐨 𝐞 𝐜𝐨 𝐞
(𝐐𝐜 )𝐞 = = = 𝐊𝐜
𝐜 𝐚 𝐜 𝐛 𝐜 𝛎𝐁
( 𝐜𝐀 ) ( 𝐜𝐁 ) ∏𝐁,𝐫𝐞𝐚𝐜𝐭 ( 𝐁 )
𝐨 𝐞 𝐨 𝐞 𝐜𝐨 𝐞

(𝐱 𝐌 )𝐞𝐦 (𝐱 𝐍 )𝐞𝐧 ∏𝐁,𝐩𝐝𝐭(𝐱 𝐁 )𝛎𝐞𝐁

(𝐐𝐱 )𝐞 = = = 𝐊𝐱
(𝐱 𝐀 )𝐚𝐞 (𝐱 𝐁 )𝐞𝐛 ∏𝐁,𝐫𝐞𝐚𝐜𝐭(𝐱 𝐁 )𝛎𝐞𝐁

𝐕𝐚𝐧𝐭 𝐡𝐨𝐟𝐟 𝐢𝐬𝐨𝐭𝐡𝐞𝐫𝐦

PB νB
∏B(Pdt) ( )
̃ ̃ 0 P0
∆r G = ∆r G + RTln
P νB
∏B(React) ( B )
P0
0
̃ = ∆r G
Case - I: At the start of the reaction ∆r G ̃ 0 + RTln
P νB
∏B(React)( B )
P0
̃ = −∞
for the reaction to be feasible, ln0 = −∞,∆r G
P νB
∏B(Pdt)( B )
̃ = ∆r G
Case - II: At the start of the reaction ∆r G ̃ 0 + RTln P0
0
̃ = +∞
if the backward reaction doesnot proceed, ∆r G

Case-III: At some intermediate state, the two terms in R.H.S. will cancel each otherto make the reaction is
at equilibrium.

PB νB
The term ∏B ( ) is known as standard reaction quotient which is denoted by 𝐐𝐏 .
P0
At equilibrium, (𝐐𝐏 ) = 𝐊𝐏 , which is known as the standard equilibrium constant.
eq
 ̃ = ∆r G
so the equation∆r G ̃ 0 + RTln𝐐 becomes,
𝐏
̃𝟎 = −𝐑𝐓𝐥𝐧𝐊𝐏
∆𝐫 𝐆
This is known as Reaction Isotherm
Using both the two equation we can write,
̃ = −𝐑𝐓𝐥𝐧𝐊 𝐏 + 𝐑𝐓𝐥𝐧𝐐𝐏
∆𝐫 𝐆

𝐐𝐏
̃ = 𝐑𝐓𝐥𝐧
∆𝐫 𝐆
𝐊𝐏

Case-1 𝐐𝐏 > 𝐊 𝐏 ̃>0

∆r G Non spontaneous
Case-2 𝐐𝐏 < 𝐊 𝐏 ̃<0
∆r G Spontaneous
Case-3 𝐐𝐏 = 𝐊 𝐏 ̃=0
∆r G Equilibrium

Define reaction isobar and arrive the equation in differential and integrated form

From the definition of free energy change we can write

∆G = −RTln K P + RT ∑ υ ln P … … . (1)
Dividing both side with T
∆G⁄ = −Rln K + R ∑ υ ln P … … . (2)
T P

Differentiating equation with respect to T at constant P

∂∆G ∂ ln K P ∂ ∑ υ ln P
( ) = −R ln K P − RT ( ) + R ∑ υ ln P + RT ( )
∂T P ∂T P ∂T P
∂∆G ∂ ln K P
( ) = −R ln K P + R ∑ υ ln P − RT ( )
∂T P ∂T P
Using equation (2)
∂∆G ∂ ln K P
( ) = ∆G⁄T − RT ( ) … … (3)
∂T P ∂T P
Multiplying equation (3) with T
∂∆G ∂ ln K P
T( ) = ∆G − RT 2 ( ) … … . . (4)
∂T P ∂T P
From the thermodynamic equation of state for finite change in process,
d∆G = −∆SdT + ∆VdP at constant P, so we can write
∂∆G
( ) = −∆S … … . (5)
∂T P
From Gibbs Helmholtz equation, ∆G = ∆H − T∆S, so using the equation (5)
∂∆G
∆G = ∆H + T ( ) … . (6)
∂T P
Using (6) in (4)
 ∂ ln K P
−∆H = −RT 2 ( )
∂T P
𝛛 𝐥𝐧 𝐊 𝐏 ∆𝐇
( ) = … … … (7)
𝛛𝐓 𝐏 𝐑𝐓 𝟐
As ∆H is measured at constant P, the above reaction is called Reaction Isobar
From the dependence of K P and K x
PT ∆υg
KP = Kx ( )
P0
PT
ln K P = ln K x + ∆υg ln ( )
P0
Differentiating with respect to T at const P
∂ ln K P ∂ ln K x
( ) =( )
∂T P ∂T P
Hence equation (7) becomes,
∂ ln K x ∆H
( ) = … … (8)
∂T P RT 2
Then the equation (7) and (8) are called the differential form of reaction isobar, where ∆H is
measured at constant P,
∆H
d ln K P = dT
RT 2
KP2 T2
∆H 𝐊 𝐏𝟐 ∆𝐇 𝟏 𝟏
∫ d ln K P = ∫ dT or, 𝐥𝐧 = [ − ]
R 𝐊 𝐏𝟏 𝐑 𝐓𝟏 𝐓𝟐
KP1 T1
The equation can also be written as,
𝐊 𝐱𝟐 ∆𝐇 𝟏 𝟏
𝐥𝐧
= [ − ]
𝐊 𝐱𝟏 𝐑 𝐓𝟏 𝐓𝟐
This is the integrated form of Reaction Isobar

Q. Derive the differential and integrated form of reaction isochore

From the dependence of K P and K c , we can write,

c0 RT ∆υg 1mole
KP = Kc ( ) assuming c0 = , P0 = 1 atm
P0 lit
K P = K c (RT)∆υg , ln K P = ln K c + ∆υg ln RT = ln K c + ∆υg ln R + ∆υg ln T
Differentiating with respect to T, we can write,
dlnK P dlnK c ∆υg
= +
dT dT T
Using reaction isobar we can write,
∆H 0 dlnK c ∆υg dlnK c ∆H 0 ∆υg
= + or, = −
RT 2 dT T dT RT 2 T
 dlnK c ∆H 0 − ∆υg RT
= … … (1)
dT RT 2
From the thermo chemical equation,∆H 0 = ∆E 0 + ∆υg RT
Using this equation in equation (1)
𝐝𝐥𝐧K c ∆𝐄𝟎
=
𝐝𝐓 𝐑𝐓 𝟐
This is the differential form of Reaction Isochore, If ∆E 0 is independent of T, then integrating the
above equation we can write,
∆E 0
d ln K c = dT
RT 2
Kc2 T2
∆E 0 K c2 ∆E 0 1 1
∫ d ln K P = ∫ dT or, ln = [ − ]
R K c1 R T1 T2
Kc1 T1
The equation can also be written as,
K c2 ∆𝐄𝟎 𝟏 𝟏
𝐥𝐧 ln = [ − ]
K c1 𝐑 𝐓𝟏 𝐓𝟐
This is the integrated form of Reaction Isochors

From Vant Hoff isotherm establish Vant Hoff isobar at standard condition

̃ 0 = −RT ln 𝐊 𝐏
∆r G
̃0
∆r G
= −R ln 𝐊 𝐏
T
Differentiating with respect to T at constant P
∂ ∆r G̃0 ∂ ln 𝐊 𝐏
[ ( )] = −R ( ) … . . (1)
∂T T P
∂T P
From Gibbs Helmholtz equation
̃0
∂ ∆r G ̃0
∆r H
[ ( )] = − 2
∂T T P
T
Putting the value in equation (1)
∂ ln 𝐊 𝐏 ∆r H̃0
−R ( ) =− 2
∂T P T
∂ ln 𝐊 𝐏 ̃
∆r H 0
( ) =
∂T P RT 2
Plot of KP vs 𝟏⁄𝐓

∂ ln 𝐊 𝐏 ̃0
∆r H
( ) = can be represented by
∂T P RT 2
̃0
∆r H ∆r H̃0 1
d ln 𝐊 𝐏 = dT = − d( )
RT 2 R T
d ln 𝐊 𝐏 ̃
∆r H 0
=−
1 R
d (T)
1 ̃0
∆r H
So the slope of ln 𝐊 𝐏 vs T depends on − R
̃ 0 = (−)ve and for endothermic reaction ∆r H
For exothermic reaction ∆r H ̃ 0 = (+)ve
 Q. From the following reaction prove that the partial pressure of 𝐍𝐎𝟐 is directly
proportional to the 3/2rd power of total pressure P. Also prove that with increase of
total pressure at equilibrium, formation of 𝐍𝐎𝟐 will increase. Given 𝐍𝟐 + 𝟐𝐎𝟐 ⇌ 𝟐𝐍𝐎𝟐

Reaction 𝐍𝟐 + 𝟐𝐎𝟐 ⇌ 𝟐𝐍𝐎𝟐

Stoichiometry Coefficient (𝛄𝐢 ) −𝟏 −𝟐 +𝟐
Initial mole (𝐧𝐢 ) 𝟏 𝟐 𝟎
Equilibrium mole (𝐧𝐭 ) 𝟏−𝛏 𝟐 − 𝟐𝛏 𝟐𝛏
Total mole = 𝟏 − 𝛏 + 𝟐 − 𝟐𝛏 + 𝟐𝛏 = 𝟑 − 𝛏
Mole fraction(𝐱 𝐢 ) 𝟏−𝛏 𝟐 − 𝟐𝛏 𝟐𝛏
𝟑−𝛏 𝟑−𝛏 𝟑−𝛏
Partial pressure (𝐏𝐢 ) 𝟏−𝛏 𝟐 − 𝟐𝛏 𝟐𝛏𝐏
( )𝐏 ( )𝐏
𝟑−𝛏 𝟑−𝛏 𝟑−𝛏

For table we can write, PO2 = 2PN2

2 2 2
PNO2
PNO 2
PNO 2
KP = = 2 or, 4K P = … … . (1)
PN2 PO22 PN2 (2PN2 ) PN32
2ξP 2
() 4ξ2 P 2 (3 − ξ)3
3−ξ
4K P = = ×
1 − ξ 3 (3 − ξ)2 (1 − ξ)3 P 3
( P)
3−ξ
ξ2 (3 − ξ)
KP =
(1 − ξ)3 P
3ξ2
for low conversion(3 − ξ) ≈ 3; (1 − ξ) ≈ 1or, KP =
P
To maintain the K P constant, with increasing total pressure, ξ increases at equilibrium, Hence
the formation of NO2 will increase,

PT = PNO2 + PO2 + PN2 , or, PT = PNO2 + 3PN2

PT − PNO2
PN2 = ( )
3
Putting the value in equation (1)
2
27PNO2
4K P = 3
(PT − PNO2 )
For low conversion, PT − PNO2 ≈ PT
2
27PNO 2
4
4K P = 2
or, PNO = K P PT3
PT3 2
27
 2 3⁄
2
PNO2 = √K P PT
3√3

Q. At 2000K, the standard free energy change for the reaction, 𝐍𝟐 + 𝐎𝟐 ⇌ 𝟐𝐍𝐎, is given by
∆𝐆𝟎 = 𝟐𝟐𝟖𝟎𝟎 − 𝟐. 𝟓𝐓.
Calculate 𝐊 𝐏 at this temperature and the degree of dissociation (where ∆𝐆𝟎 is in
cal/mole)
cal
∆G0 = 22800 − 2.5T = 22800 − (2.5 × 2000) = 17800 mole
∆G0
From the vant hoff method, ∆G0 = −RT ln K P or, K P = exp (− )
RT

17800 cal/mole
K P = exp (− ) = 0.0113
cal
1.987 × 2000K
K mole

Reaction 𝐍𝟐 + 𝐎𝟐 ⇌ 𝟐𝐍𝐎
Initial mole (ni ) 1 1 0
Equilibrium mole (nt ) 1−ξ 1−ξ 2ξ
Total mole = 1 − ξ + 1 − ξ + 2ξ = 2
Mole fraction(xi ) 1−ξ 1−ξ 2ξ
2 2 2
Partial pressure (Pi ) 1−ξ 1−ξ 2ξP
( )P ( )P
2 2 2
2ξP 2
2
PNO ( 2 ) 4ξ2
KP = = =
PN2 PO2 1 − ξ 2 (1 − ξ)2
( 2 P)
For low conversion, 1 − ξ ≈ 1
KP
4ξ2 = K P or, ξ2 = , or, ξ = 0.053
4

Q. For ozone at 250C, ∆𝐆𝐟𝟎 = 𝟏𝟔𝟑. 𝟐 𝐤𝐉/𝐦𝐨𝐥

a) At 250C, compute the equilibrium constant 𝐊 𝐏 for the reaction
𝟑𝐎𝟐 (𝐠) ⇌ 𝟐𝐎𝟑 (𝐠)
b) Assuming that the advancement at equilibrium, 𝛏𝐞 , is very much less than unity, show that
𝟑
𝛏𝐞 = √𝐏𝐊 𝐏
𝟐
(Let the original number of moles of 𝐎𝟐 be three, and of 𝐎𝟑 be zero)
c) Calculate Kx at 5 atm and Kc
a) The standard free energy change of the reaction
0 0
∆G0 = 2∆Gf,O 3
− 3∆Gf,O 2
= 2(163.2 × 103 J/mol)
 Now using Vant Hoff isotherm
∆G = −RT ln K P = 326.4 × 103 J/mol
0

−8.314JK −1 mole−1 × (298K) ln K P = 326.4 × 103 Jmol−1 or, K P = 6 × 10−58

3O2 (g) ⇌ 2O3 (g)
Initial mole 3 0
Moles at equilibrium 3 − 3ξe 2ξe
Total mole at equilibrium (3 − 3ξe ) + 2ξe = 3 − ξe
Mole fraction (3 − 3ξe ) 2ξe
(3 − ξe ) (3 − ξe )
Partial pressure (3 − 3ξe ) 2ξe P
P
(3 − ξe ) (3 − ξe )
Now,
2ξe P 2
{ } 4ξ2e (3 − ξe )
PO23 (3 − ξe )
KP = ⁄ 3 = =
PO2 (3 − 3ξe ) 3 (3 − 3ξe )3 P
{ P}
(3 − ξe )
As ξe ≪ 1, so we can approximate (3 − ξe ) ≈ 3 or (3 − 3ξe ) ≈ 3
4ξ2e × 3 4ξ2e
KP = =
27P 9P
9 3
ξ2e = PK P or, ξe = √PK P
4 2
We know that
C0 RT ∆n
KP = KC ( )
P0
Here ∆n = 2 − 3 = −1
−1
1 molelit−1 ×0.0821lit atmK−1 mol−1 ×298K
6 × 10−58 = K C ( )
1atm
We know that
P ∆n P −1
KP = Kx ( ) = Kx ( )
P0 P0
P 5 atm
K x = K P ( ) = 6 × 10−58 ( ) = 30 × 10−58
P0 1atm

Q. Whether the reaction 𝐍𝟐 𝐎𝟒 ⇌ 𝟐𝐍𝐎𝟐 is feasible or not when both are at 1 atm and 250C? If 𝐍𝐎𝟐 is
to be produced at 1 atm what must be the minimum pressure of 𝐍𝟐 𝐎𝟒 ? How can 𝐍𝐎𝟐 be produced
spontaneously at 250C? Given
𝟎
∆𝐆𝐟,(𝐍𝟐 𝐎𝟒 ,𝐠)
= 𝟐𝟑. 𝟔𝟏𝟗𝐤𝐂𝐚𝐥𝐦𝐨𝐥𝐞−𝟏
𝟎
∆𝐆𝐟,(𝐍𝐎𝟐 ,𝐠)
= 𝟏𝟐. 𝟑𝟗𝐤𝐂𝐚𝐥𝐦𝐨𝐥𝐞−𝟏
According to the given problem
 N2 O4 ⇌ 2NO2
The standard free energy change of the reaction
0 0
∆G0 = 2∆Gf,(NO 2 ,g)
− ∆Gf,(N 2 O4 ,g)
∆G0 = (2 × 12.39) − 23.619 = 1.161kCalmole−1
From the (+)ve value of ∆G0 we cannot say anything about the spontaneity of a reaction. The
spontaneity of a reaction is best described from the value of ∆G
∆G = ∆G0 + RT ln QP
2
0
PNO 2
∆G = ∆G + RT ln
PN2 O4
Case 1. If both N2 O4 and NO2 are present at 1 atm pressure then,
11
∆G = 1161Calmole−1 + RT ln = (+)ve
1
Hence the reaction will be non-spontaneous
Case 2. Now NO2 has been produced with a pressure at 1 atm, then the equation becomes

−1
11
∆G = 1161Calmole + RT ln
PN2O4
At first we have to find out the equilibrium pressure of N2 O4 where ∆G = 0, then putting the
value of ∆G0 in the equation
11
0 = 1161Calmole−1 + 1.987CalK −1 mole−1 × 298K × ln
PN2O4
PN2 O4 = 7.105
Hence the reaction is spontaneous at a pressure greater than 7.105 atm

Q. For the reaction at 250C, 𝐏𝐂𝐥𝟓 (𝐠) ⇌ 𝐏𝐂𝐥𝟑 (𝐠) + 𝐂𝐥𝟐 (𝐠), ∆𝐇 = 𝟐𝟐𝐊𝐜𝐚𝐥𝐦𝐨𝐥𝐞−𝟏 . Calculate 𝐊 𝐏 at
250C and 6000C, assuming ∆𝐇 to be independent of temperature. Give standard free
energy of formation,
𝟎
∆𝐆𝐟 (𝐊𝐜𝐚𝐥𝐦𝐨𝐥𝐞−𝟏 )𝐚𝐭250C, 𝐂𝐥𝟐 (𝐠) = 𝟎. 𝟎𝟎, 𝐏𝐂𝐥𝟑 (𝐠) = −𝟔𝟖. 𝟒𝟐𝐚𝐧𝐝𝐏𝐂𝐥𝟓 (𝐠) = −𝟕𝟕. 𝟔

We can write that

0 0 0
∆G0 = ∆GPCl 3 (g)
+ ∆GCl 2 (g)
− ∆GPCl 5 (g)
= −68.42 + 0.00 + 77.6 = 9.18Kcalmole−1
0
From Vant Hoff isotherm, ∆G25 0 C = −RT ln K P,250 C

Putting the value in the above equation,

9180 calmole−1 = −1.987calK −1 mole−1 × 298K ln K P,250 C
K P,250 C = 1.85 × 10−7
Using Vant Hoff isobar,
K P,6000 C ∆H 1 1
ln =− [ − ]
K P,250 C R T2 T1
 K P,6000 C 22000 calmole−1 1 1
ln −7
= − −1 −1
[ − ]
1.85 × 10 1.987calK mole 873K 298K
K P,6000 C = 7.853 × 103

Q. In the gaseous reaction 𝟐𝐀 + 𝐁 ⇌ 𝐀 𝟐 𝐁, ∆𝐆𝟎 = −𝟏𝟐𝟎𝟎𝐂𝐚𝐥 𝐚𝐭 𝟓𝟎𝟎𝐊, What total pressure is

necessary to convert 60% of A into 𝐀 𝟐 𝐁 when A and B are in the molar ratio 1:2.

Reaction 𝟐𝐀 + 𝐁 ⇌ 𝐀𝟐𝐁
Initial mole (𝐧𝐢 ) 𝟏 𝟐 𝟎
Equilibrium mole (𝐧𝐭 ) 𝟏−𝟐∝ 𝟐−∝ ∝
Total mole = 𝟏 − 𝟐 ∝ +𝟐−∝ +∝= 𝟑 − 𝟐 ∝
Partial pressure (𝐏𝐢 ) 𝟏−𝟐∝ 𝟐−∝ ∝𝐏
( )𝐏 ( )𝐏
𝟑−𝟐∝ 𝟑−𝟐∝ 𝟑−𝟐∝
∆G0
From the vant hoff method, ∆G0 = −RT ln K P,500K or, K P,500K = exp (− )
RT

−1200 cal/mole
K P,500K = exp (− ) = 3.346
cal
1.987 × 500K
K mole
∝P
PA B 3−2∝ ∝ (3 − 2 ∝)2 1
K P,500K = 2 2 = 2 = 2
× 2
PA × PB 1−2∝ 2−∝ (1 − 2 ∝) × (2−∝) P
(3 − 2 ∝ P) × (3 − 2 ∝ P)
∝ (3 − 2 ∝)2 1
3.346 = ×
(1 − 2 ∝)2 × (2−∝) P 2

Here, 2α = 0.60, α = 0.3

Putting the value in the equation

2
0.3 (3 − 2 × 0.3 )2 1
P = × = 1.378 atm
(1 − 2 × 0.3 )2 × (2 − 0.3 ) 3.346

Q. 20.85 gm of 𝐏𝐂𝐥𝟓 (𝐠) is taken in a 4 lit closed vessel at 𝟐𝟓𝟎𝟎 𝐂. The equilibrium pressure of
the mixture is found to be 1.825 atm. Find out the partial pressure of 𝐂𝐥𝟐 and the value of 𝐊 𝐏
20.85 gm
Number of moles of PCl5 = 208.5 gm mole−1 = 0.1 mole

PCl5 (g) ⇌ PCl3 (g) + Cl2 (g)

PCl5 (g) ⇌ PCl3 (g) + Cl2 (g)
1−α α α
Number of moles at equilibrium =1 − α + α + α = 1 + α
If we start with 1 mole of PCl5 then we get 1 + α mole at equilibrium, and if we start with 0.1
mole then we will get 0.1(1 + α)
Assuming the equilibrium mixture behaves ideally,
PV = 0.1(1 + α)RT
PV 1 1.825 atm × 4 lit
1+α= × = = 1.702
RT 0.1 mole 0.0821 lit atm K −1 mole−1 × 523K × 0.1 mole
α = 0.702
αP 0.702
PPCl3 = PCl2 = = × 1.825 atm = 0.753 atm
1 + α 1.702
PPCl5 = 1.825 − (2 × 0.753 ) = 0.319 atm
0.753 × 0.753
KP = = 1.78
0.319

Dissociation of 𝐂𝐎𝟐

𝟐𝐂𝐎𝟐 (𝐠) ⇌ 𝟐𝐂𝐎(𝐠) + 𝐎𝟐 (𝐠)

Initial mole 2 0 0
Moles at equilibrium 𝟐 − 𝟐𝛏𝐞 𝟐𝛏𝐞 𝛏𝐞
Total mole at equilibrium (𝟐 − 𝟐𝛏𝐞 ) + 𝟐𝛏𝐞 + 𝛏𝐞 = 𝟐 + 𝛏𝐞
Mole fraction (𝟐 − 𝟐𝛏𝐞 ) 𝟐𝛏𝐞 𝛏𝐞
(𝟐 + 𝛏𝐞 ) (𝟐 + 𝛏𝐞 ) (𝟐 + 𝛏𝐞 )
Partial pressure (𝟐 − 𝟐𝛏𝐞 ) 𝟐𝛏𝐞 𝐏 𝛏𝐞 𝐏
𝐏
(𝟐 + 𝛏𝐞 ) (𝟐 + 𝛏𝐞 ) (𝟐 + 𝛏𝐞 )
Now,
2ξe P 2 ξe P
2 { } ξ3e P
(PCO × PO2 ) (2 + ξe ) (2 + ξe )
KP = ⁄2 = =
PCO2 (2 − 2ξe ) 2 (2 + ξe )(1 − ξe )2
{ P}
(2 + ξe )
Taking ξe ≪ 1
1
ξ3e P 2K P ⁄3
KP = or, ξe = ( )
2 P
In order to keep K P fixed with increase of pressure at equilibrium ξe decreases that is the
reaction shifted to backward direction
Sodium dimerisation reaction

𝐍𝐚(𝐠) ⇌ 𝟏
𝐍𝐚 (𝐠)
𝟐 𝟐
Initial mole 1 0
Moles at equilibrium 𝟏 − 𝛏𝐞 𝟏
𝛏
𝟐 𝐞
Total mole at equilibrium 𝟏 𝟏
(𝟏 − 𝛏𝐞 ) + 𝛏𝐞 = 𝟏 − 𝛏𝐞
𝟐 𝟐
Mole fraction (𝟏 − 𝛏𝐞 ) 𝛏𝐞
𝛏 𝛏
(𝟏 − 𝟐𝐞 ) 𝟐 (𝟏 − 𝟐𝐞 )
Partial pressure (𝟏 − 𝛏𝐞 ) 𝛏𝐞 𝐏
𝐏
𝛏 𝛏
(𝟏 − 𝟐𝐞 ) 𝟐 (𝟏 − 𝟐𝐞 )
1
2
ξe P 1
{ }
1 ξe ξe P 2 1
2
PNa 2 (1 − 2 ) { } 1
ξe2 (2 − ξe ) ⁄2
2⁄
(2 − ξe )
KP = PNa = = = 1⁄
(1 − ξe ) 2(1 − ξe )
P P 2(1 − ξe )P 2
ξ (2 − ξe )
(1 − e )
2

Taking ξe ≪ 1
1
ξe2
KP = 1⁄
(2P) 2

In order to keep K P fixed with increase of pressure at equilibrium ξe increases that is the
reaction shifted to forward direction

Formation of Nitrous oxide (NO)

𝐍𝟐 (𝐠) 𝐎𝟐 (𝐠)
+ ⇌ 𝟐𝐍𝐎(𝐠)
Initial mole 1 1 0
Moles at equilibrium 𝟏 − 𝛏𝐞 𝟏 − 𝛏𝐞 𝟐𝛏𝐞
Total mole at equilibrium (𝟏 − 𝛏𝐞 ) + (𝟏 − 𝛏𝐞 ) + 𝟐𝛏𝐞 = 𝟐
Mole fraction (𝟏 − 𝛏𝐞 ) (𝟏 − 𝛏𝐞 ) 𝟐𝛏𝐞
𝟐 𝟐 𝟐
Partial pressure (𝟏 − 𝛏𝐞 ) (𝟏 − 𝛏𝐞 ) 𝟐𝛏𝐞 𝐏
𝐏 𝐏
𝟐 𝟐 𝟐
 2ξ P 2
2
PNO ( 2e ) 4ξ2e
KP = = =
PN2 × PO2 1−ξ 1−ξ (1 − ξ2e )
( 2 e P) ( 2 e P)

In order to keep K P fixed with increase of pressure at equilibrium ξe remains unchanged that is the
reaction does not shifted to either forward or backward direction

Dissociation of NH4HS (s)

Let n0 be the initial moles of NH4HS (s), ξe is the equilibrium advancement of the reaction

ξe⁄
α= n0

NH4 Cl(s) ⇌ NH3 (g) + HCl(g)

Initial mole 𝐧𝟎 0 0
Moles at equilibrium 𝐧𝟎 − 𝛏𝐞 𝛏𝐞 𝛏𝐞
Total mole at equilibrium (𝐧𝟎 − 𝛏𝐞 ) + 𝛏𝐞 + 𝛏𝐞 = 𝐧𝟎 + 𝛏𝐞
Mole fraction (𝐧𝟎 − 𝛏𝐞 ) 𝛏𝐞 𝛏𝐞
(𝐧𝟎 + 𝛏𝐞 ) (𝐧𝟎 + 𝛏𝐞 ) (𝐧𝟎 + 𝛏𝐞 )
𝛏 (𝟏 − 𝛂) 𝛂 𝛂
Expressing in 𝛂 ( 𝐞⁄𝐧𝟎 )
(𝟏 + 𝛂) (𝟏 + 𝛂) (𝟏 + 𝛂)
Partial pressure − 𝛂𝐏 𝛂𝐏
(𝟏 + 𝛂) (𝟏 + 𝛂)
αP αP α2 P 2
K P = PNH3 × PHCl = ( )( )=
1+α 1+α (1 + α)2
Taking α ≪ 1, so K P becomes
1
(K P )2
K P = α2 P 2 or, α =
P
In order to keep K P fixed with increase of pressure at equilibrium α decreases that is the reaction
shifted to backward direction

Dissociation of NH2COO NH4 (s)

 NH2COO NH4(s) ⇌ 𝟐𝐍𝐇𝟑 (𝐠) + 𝐂𝐎𝟐 (𝐠)
Initial mole 𝐧𝟎 0 0
Moles at equilibrium 𝐧𝟎 − 𝛏𝐞 𝟐𝛏𝐞 𝛏𝐞
Total mole at equilibrium (𝐧𝟎 − 𝛏𝐞 ) + 𝟐𝛏𝐞 + 𝛏𝐞 = 𝐧𝟎 + 𝟐𝛏𝐞
Mole fraction (𝐧𝟎 − 𝛏𝐞 ) 𝟐𝛏𝐞 𝛏𝐞
(𝐧𝟎 + 𝟐𝛏𝐞 ) (𝐧𝟎 + 𝟐𝛏𝐞 ) (𝐧𝟎 + 𝟐𝛏𝐞 )
𝛏 (𝟏 − 𝛂) 𝟐𝛂 𝛂
Expressing in 𝛂 ( 𝐞⁄𝐧𝟎 )
(𝟏 + 𝟐𝛂) (𝟏 + 𝟐𝛂) (𝟏 + 𝟐𝛂)
Partial pressure − 𝟐𝛂𝐏 𝛂𝐏
(𝟏 + 𝟐𝛂) (𝟏 + 𝟐𝛂)
From partial pressure, PNH3 = 2PCO2
Total pressure PT = PNH3 + PCO2 = 2PCO2 + PCO2 = 3PCO2
2 2
3
K P = PNH 3
× PCO2 = (2PCO2 ) × PCO2 = 4PCO2

PT 3 4 3
KP = 4 ( ) = P
3 27 T

Dissociation of Nitrogen dioxide

NO2 (g) ⇌ 𝐍𝐎(𝐠) + 𝟏
𝐎 (𝐠)
𝟐 𝟐
Initial mole 𝐧𝟎 0 0
Moles at equilibrium 𝐧𝟎 − 𝛏𝐞 𝛏𝐞 𝟏
𝛏
𝟐 𝐞
Total mole at equilibrium 𝟏 𝟏
(𝐧𝟎 − 𝛏𝐞 ) + 𝛏𝐞 + 𝛏𝐞 = 𝐧𝟎 + 𝛏𝐞
𝟐 𝟐
Mole fraction (𝐧𝟎 − 𝛏𝐞 ) 𝛏𝐞 𝛏𝐞
𝟏 𝟏 𝟏
(𝐧𝟎 + 𝟐 𝛏𝐞 ) (𝐧𝟎 + 𝟐 𝛏𝐞 ) 𝟐 (𝐧𝟎 + 𝟐 𝛏𝐞 )
𝛏 (𝟏 − 𝛂) 𝛂 𝛂
Expressing in 𝛂 ( 𝐞⁄𝐧𝟎 ) 𝛂 𝛂
𝛂 (𝟏 + 𝟐) 𝟐 (𝟏 + 𝟐)
(𝟏 + 𝟐)
Partial pressure (𝟏 − 𝛂) 𝟐𝛂𝐏 𝛂𝐏
𝟐 𝐏
(𝟐 + 𝛂) (𝟐 + 𝛂) (𝟐 + 𝛂)

From partial pressure, PNO = 2PO2

1 1 3 3
αP 2 3 1
PNO PO22 (2PO2 ) × PO22 2PO22 2 (2 + α) α2 P 2
KP = = = = = 1
PNO2 PNO2 PNO2 (1 − α)
2 P (2 + α)2 (1 − α)
(2 + α)
Taking α ≪ 1, so K P becomes
3 1 2
3
α2 P 2 √2K P
KP = or, α = ( )
√2 √P
 Total pressure PT = PNO2 + PNO + PO2 = PNO2 + 3PO2
(PT − PNO2 )
3PO2 = (PT − PNO2 ) or, PO2 =
3
3
3 (PT − PNO2 ) 2
2PO22 2{ }
3 2 3
−1
KP = = or, PNO2 = 2
PNO2 PNO2 3 (PT − PNO2 ) K P
32
Since PT ≫ PNO2
2 3
PNO2 = 3 (PT )2 K P −1
32

Variation of free energy of the reaction mixture with the advancement of the
reaction
The criterion of spontaneity of a reaction, i.e. ∆GP,T < 0, does not necessarily mean that the free
energy of products in the pure state must be less than the free energy of the pure reactants for a
homogeneous reaction to proceed. This is because, products just after the formation remain with the
reactants in the mixed up state and ∆Gmix is always negative. At any instant of the reaction, the
overall free energy change ∆r G is the summation of free energy change ∆Gpure of conversion of
reactants into products and the free energy change of mixing ∆Gmix of products with the reactants,
i.e.,

∆r G = ∆Gpure + ∆Gmix
 Therefore a reaction can proceed even when ∆Gpure is positive provided ∆Gmix is numerically
greater than ∆Gpure so that over all ∆r G becomes negative. With the progress of the reaction the
overall free energy of the reaction mixture decreases and at equilibrium free energy becomes
minimum. Therefore free energy versus advancement (ξ) of reaction plot passes through a
minima.

Reactions where products have lower free energy than the reactants, equilibrium condition lies
to the towards the products, i.e., the equilibrium advancement become high where as in case of
reactions where products have higher free energy than the reactants, the equilibrium condition
lies towards the reactants and equilibrium advancement will be low.

Expression of G and the condition of equilibrium

Let us consider that the gas phase reaction

𝐦𝐀 + 𝐧𝐁 → 𝐫𝐂 + 𝐪𝐃
occur at constant pressure P and temperature T. Therefore the free energy of the mixture at that instant is,
𝐆 = ∑ 𝐧𝐢 𝛍𝐢 = ∑ 𝐧𝐢 (𝛍∗𝐢 + 𝐑𝐓 𝐥𝐧 𝐱 𝐢 ) = ∑ 𝐧𝐢 𝛍∗𝐢 + 𝐑𝐓 ∑ 𝐥𝐧 𝐱 𝐢
The first term ∑ 𝐧𝐢 𝛍∗𝐢 represents the summation of free energy of that number of moles of pure
constituents at pressure P and temperature T as are present in the mixture and is represented by 𝐆𝐩𝐮𝐫𝐞 .
The second term of the equation defines free energy change due to mixing of the constituents and is
represented by ∆𝐆𝐦𝐢𝐱 .
Hence the equation is represented by
(𝐆𝐏,𝐓 𝐨𝐫 𝐆) = 𝐆𝐏𝐮𝐫𝐞(𝐏,𝐓) + ∆𝐆𝐦𝐢𝐱
𝛛𝐆 𝛛𝐆𝐏𝐮𝐫𝐞 𝛛∆𝐆𝐦𝐢𝐱
∆𝐫 𝐆 = ( ) = ( ) +( )
𝛛𝛏 𝐓,𝐏 𝛛𝛏 𝐓,𝐏 𝛛𝛏 𝐓,𝐏
𝛛𝐆
𝐀𝐭 𝐞𝐪𝐮𝐢𝐥𝐢𝐛𝐫𝐢𝐮𝐦, ∆𝐫 𝐆 = 𝟎, ( ) = 𝟎
𝛛𝛏 𝐓,𝐏
𝛛𝐆𝐏𝐮𝐫𝐞 𝛛∆𝐆𝐦𝐢𝐱
( ) = −( )
𝛛𝛏 𝐓,𝐏 𝛛𝛏 𝐓,𝐏

mA + nB → rC + qD
t=0 m n 0 0
t=t m(1 − ξ) n(1 − ξ) rξ qξ

𝐆𝐩𝐮𝐫𝐞 = 𝐦(𝟏 − 𝛏)𝛍∗𝐀 + 𝐧(𝟏 − 𝛏)𝛍∗𝐁 + 𝐫𝛏𝛍𝐂∗ + 𝐪𝛏𝛍𝐃

∗

Hence Gpure is a linear function of ξ,

when 𝛏 = 𝟎, 𝐆𝐩𝐮𝐫𝐞 = 𝐦𝛍∗𝐀 + 𝐧𝛍∗𝐁 = 𝐆𝐫𝐞𝐚𝐜𝐭𝐚𝐧𝐭 and when 𝛏 = 𝟏, 𝐆𝐩𝐮𝐫𝐞 = 𝐫𝛍∗𝐂 + 𝐪𝛍∗𝐃 = 𝐆𝐩𝐫𝐨𝐝𝐮𝐜𝐭
Section A
∂GPure
( ) = negative always
∂ξ T,P
∂∆Gmix
( ) = (−)ve then 0 then (+)ve
∂ξ T,P
∂G ∂GPure ∂∆Gmix
( ) =( ) +( ) = (−)ve
∂ξ T,P ∂ξ T,P ∂ξ T,P
Section B
∂GPure
( ) = negative always
∂ξ T,P
∂∆Gmix
( ) = highly (+)ve
∂ξ T,P
∂G ∂GPure ∂∆Gmix
( ) =( ) +( ) = (+)ve
∂ξ T,P ∂ξ T,P ∂ξ T,P

Q. At high temperature 𝐂𝐎𝟐 dissociates according to the equation 𝟐𝐂𝐎𝟐 = 𝟐𝐂𝐎 + 𝐎𝟐 . At

one atmospheric pressure the fraction of 𝐂𝐎𝟐 dissociates is 𝟐 × 𝟏𝟎−𝟓 at 1000K and at
1400K it is 𝟏. 𝟐𝟕 × 𝟏𝟎−𝟐. Assuming that ∆𝐇 of the reaction is independent of temperature,
Calculate ∆𝐆𝟎 and ∆𝐒 𝟎
 𝟐𝐂𝐎𝟐 ⇌ 𝟐𝐂𝐎 + 𝐎𝟐

𝟐 𝟎 𝟎

𝟐−𝟐∝ 𝟐∝ ∝

Total number of moles at equilibrium = 2+∝

2(1−∝)P 2∝P ∝P
PCO2 = , PCO = , PO2 =
2+∝ 2+∝ 2+∝
4 ∝2 P 2 ∝ P
× ∝3 P ∝3 P
(2+∝)2 2+∝
KP = = as ∝≪ 1 or, K P =
4(1−∝)2 P 2 (2+∝)(1−∝)2 2
(2+∝)2
K P,1400K ∆H 1 1
ln =− [ − ]
K P,1000K R T2 T1
∝1400 3 ∆H 1 1
ln ( ) =− −1 −1
[ − ]
∝1000 1.987calK mole 1400K 1000K
3
1.27 × 10−2 ∆H 1 1
ln ( −5
) =− −1 −1
[ − ]
2 × 10 1.987calK mole 1400K 1000K
∆H = 134.645 Kcalmole−1
3
(2×10−5 ) ×1
At, 1000K, K P = = 4 × 10−5
2
0
∆G1000K = −(1.987calK −1 mole−1 ) × (1000K) ln 4 × 10−5 = 65.874 KCalmole−1
0 0
0
∆H1000K − ∆G1000K (134.645 − 65.874) × 103 Calmole−1
∆S1000K = = = 68.771CalK −1 mole−1
T 1000K

Q. For the gaseous reaction 𝐂𝟐 𝐇𝟐 + 𝐃𝟐 𝐎 ⇌ 𝐂𝟐 𝐃𝟐 + 𝐇𝟐 𝐎; ∆𝐇 is 530 𝐂𝐚𝐥𝐦𝐨𝐥𝐞−𝟏 . At 250C, 𝐊 𝐏

is 0.82. Calculate how much 𝐂𝟐 𝐃𝟐 will be formed if 1 mole of 𝐂𝟐 𝐇𝟐 and 2 mole of 𝐃𝟐 𝐎 are
put together at a total partial pressure of 1 atm and at 1000C.

For the reaction, C2 H2 + D2 O ⇌ C2 D2 + H2 O

From the Vant Hoff isobar,
K P,373K 530Calmole−1 1 1
ln =− [ − ]
K P,298K 1.987calK −1 mole−1 373K 298K
Given, K P,298K = 0.82 using the above equation, K P,373K = 0.982

C2 H2 + D2 O ⇌ C2 D2 + H2 O
1 2 0 0
1−x 2−x x x
Total mole = 1 − x + 2 − x + x + x = 3
1−x 2−x x x
PC2 H2 = P, PD2 O = P, PC2D2 = P, PH2 O = P
3 3 3 3
x x
PC D × PH2O
KP = 2 2 = 3P × 3P =
x2
= 0.982
PC2 H2 × PD2 O 1 − x P × 2 − x P (1 − x)(2 − x)
3 3
Solving, x = 0.664

𝟏 𝟏
Q. The equilibrium constant for the reaction 𝐈 (𝐠) + 𝟐 𝐁𝐫𝟐 (𝐠) → 𝐈𝐁𝐫(𝐠) can be
𝟐 𝟐
represented as,
𝟐𝟕𝟕. 𝟒
𝐥𝐨𝐠 𝐊 𝟎 = + 𝟎. 𝟑𝟖𝟏𝟏, 𝐭𝐞𝐦𝐩𝐞𝐫𝐚𝐭𝐮𝐫𝐞 = 𝟐𝟗𝟖𝐊, 𝐅𝐢𝐧𝐝, ∆𝐫 𝐆𝟎 , ∆𝐫 𝐇 𝟎 , ∆𝐫 𝐒 𝟎
𝐓
277.4
log K 0 = + 0.3811 … … … (1)
T
From integrated form of Vant Hoff reaction,
∆r H 0
log K 0 = − + I′ … … … . (2)
2.303RT
Comparing, equation (1) and (2)
∆r H 0
− = 277.4K or, ∆r H 0 = −2.303 × 277.4K × 8.314JK −1 mole−1
2.303R
∆r H 0 = −5.31 × 10−3 Jmole−1
Putting T = 298K, putting the value in equation (1)
277.4 277.4
log K 0 = + 0.3811 or, ln K 0 = 2.303 [ + 0.3811]
298 298
So, using vant hoff equation, ∆r G0 = −RT ln K 0 = −7486 Jmole−1
Using Gibbs Helmholtz equation, ∆r G0 = ∆r H 0 − T∆r S 0
Or, you can find out the value of ∆r S 0

Q. 𝐏𝐂𝐥𝟓 dissociates according to, 𝐏𝐂𝐥𝟓 (𝐠) ⇌ 𝐏𝐂𝐥𝟑 (𝐠) + 𝐂𝐥𝟐 (𝐠). At a temperature 523K, 𝐊 𝟎𝐏 =
𝟏. 𝟖𝟔. Find the density of equilibrium mixture in gm/lit at a total pressure 100 KPa. Given
standard pressure = 𝟏𝟎𝟎𝐊𝐏𝐚.

PCl5 (g) ⇌ PCl3 (g) + Cl2 (g)

1−α α α

Total mole nt = 1 − α + α + α = 1 + α
 ∝ P PT (1−∝) PT
PPCl3 = PCl2 = ( ), PPCl5 = ( )
1 + α P0 (1+∝) P0

∝ P PT ∝P P
P × P (P ) × 1 + α (PT ) ∝2 PT ∝2 100 KPa
PCl Cl 1 + α 0 0
K 0P = 3 2
= = ( ) = ( )
PPCl5 (1−∝) PT 2
(1 −∝ ) P0 2
(1 −∝ ) 100 KPa
( )
(1+∝) P0

∝2
K 0P = or, K 0P −∝2 K 0P =∝2
(1 −∝2 )

K 0P 1.86
0r, ∝= √ √
0 = 1 + 1.86 = 0.801
1 + KP

Assuming equilibrium mixture behave ideally, if we start with n mole then equilibrium total
mole = n(1+∝)

PV = n(1+∝)RT

m m PM
Or, PV = (1+∝)RT or, =
M V (1+∝)RT

m 100 × 103 Nm−2 × 208.5 gmmole−1 gm 2662.4 gm gm

= −1 −1
= 2662.4 3 = 3
= 2.6
V (1 + 0.801)8.314 NmK mole × 523K m 10 lit lit

State La-Chatelier principle and also state the effect of Pressure, Temperature and
adding component on the system

If a system at equilibrium is subjected to a change, the system will react in such a way so as to
oppose or reduce the change if this is possible. i.e., the system tends to balance or counteract
the effect of any imposed stress.
Increasing the pressure the reaction will shift in a direction where the number of gaseous
molecules is reduced. With increasing the heat, the equilibrium will shift in the endothermic
direction. By adding a new component, the reaction proceeds in a direction, so as to reduce the
amount of this component.
From the definition of reaction potential,
𝛛𝐆
∆𝐫 𝐆 = ( ) … . (𝟏)
𝛛𝛏 𝐓,𝐏
So it can be written that ∆𝐫 𝐆 = 𝐟(𝐓, 𝐏, 𝛏)
𝛛∆𝐫 𝐆 𝛛∆𝐫 𝐆 𝛛∆𝐫 𝐆
𝐝∆𝐫 𝐆 = ( ) 𝐝𝐓 + ( ) 𝐝𝐏 + ( ) 𝐝𝛏
𝛛𝐓 𝐏,𝛏 𝛛𝐏 𝐓,𝛏 𝛛𝛏 𝐓,𝐏
𝐝∆𝐫 𝐆 = −∆𝐫 𝐒𝐝𝐓 + ∆𝐫 𝐕𝐝𝐏 + 𝐆′′ 𝐝𝛏 … . . (𝟐)
Where,
𝛛 𝛛𝐆
𝐆′′ = { ( ) }
𝛛𝛏 𝛛𝛏 𝐓,𝐏
𝐓,𝐏
At equilibrium, 𝐝∆𝐫 𝐆 = 𝟎
Then the equation (2) becomes,
′′ (𝛛𝛏)
−∆𝐫 𝐒(𝛛𝐓)𝐞𝐪 + ∆𝐫 𝐕(𝛛𝐏)𝐞𝐪 + 𝐆𝐞𝐪 𝐞𝐪 = 𝟎 … … (𝟑)
Applying Gibbs Helmholtz equation,
∆𝐫 𝐇
∆𝐫 𝐆 = ∆𝐫 𝐇 − 𝐓∆𝐫 𝐒, 𝐨𝐫, ∆𝐫 𝐒 = (𝐚𝐭 𝐞𝐪𝐮𝐢𝐥𝐢𝐛𝐫𝐢𝐮𝐦)
𝐓
Putting the value in equation (3)
∆𝐫 𝐇 ′′ (𝛛𝛏)
− (𝛛𝐓)𝐞𝐪 + ∆𝐫 𝐕(𝛛𝐏)𝐞𝐪 + 𝐆𝐞𝐪 𝐞𝐪 = 𝟎
𝐓
Here in this equation, 𝐆𝐞𝐪
′′
is always a positive quantity.
At equilibrium constant Temperature,
𝛛𝛏𝐞𝐪 ∆𝐫 𝐕
( ) = − ′′ … … . . (𝟒)
𝛛𝐏 𝐓,𝐞𝐪 𝐆𝐞𝐪
At equilibrium constant Pressure,
𝛛𝛏𝐞𝐪 ∆𝐫 𝐇
( ) = ′′
… … . . (𝟓)
𝛛𝐓 𝐏,𝐞𝐪 𝐓𝐆𝐞𝐪

Effect of temperature

Nature of Sign of ∆𝐫 𝐇 Sign of Sign of Shift of equilibrium

reaction 𝐝𝐓 𝐝𝛏𝐞𝐪

(+)𝐯𝐞 (−)𝐯𝐞 Backward direction or

endothermic or high enthalpy
Exothermic (−)𝐯𝐞 side

(−)𝐯𝐞 (+)𝐯𝐞 Forward direction or exothermic

or low enthalpy side

(+)𝐯𝐞 (+)𝐯𝐞 Forward direction or

(+)𝐯𝐞 endothermic or high enthalpy
Endothermic side
 (−)𝐯𝐞 (−)𝐯𝐞 Backward direction or
exothermic or low enthalpy side

Effect of pressure
Considering the ideal gas behavior,
𝐏∆𝐫 𝐕 = ∆𝛖𝐠 𝐑𝐓
Putting the value in equation (4)
𝛛𝛏𝐞𝐪 ∆𝛖𝐠 𝐑𝐓
( ) =− ′′
𝛛𝐏 𝐓,𝐞𝐪 𝐏𝐆𝐞𝐪
Case: 1 Case: 2

If ∆𝛖𝐠 = (−)𝐯𝐞 If ∆𝛖𝐠 = (+)𝐯𝐞

𝛛𝛏𝐞𝐪 𝛛𝛏𝐞𝐪
( ) = (+)𝐯𝐞 ( ) = (−)𝐯𝐞
𝛛𝐏 𝐓,𝐞𝐪 𝛛𝐏 𝐓,𝐞𝐪

So, increasing the P, increases the extent of So, increasing the P, decreases the extent of
the reaction the reaction

Effect of addition of inert gas in equilibrium

A chemical reaction can be represented in general form as follows,

ν1 A1 + ν2 A2 → ν3 A3 + ν4 A4
where A1 and A2 are the reactant and A3 and A4 are the product, ν1 , ν2 be the stoichiometry
of the reactant and ν3 , ν4 are the product stoichiometry respectively.
𝛎𝟏 𝐀 𝟏 + 𝛎𝟐 𝐀 𝟐 → 𝛎𝟑 𝐀 𝟑 + 𝛎𝟒 𝐀 𝟒

𝛏=𝟎 𝐧𝟏 𝐧𝟐 𝐧𝟑 𝐧𝟒

𝛏 = 𝛏𝐞𝐪 𝐧𝟏 𝐧𝟐 − 𝛎𝟐 𝛏𝐞𝐪 𝛎𝟑 𝛏𝐞𝐪 𝛎𝟒 𝛏𝐞𝐪

− 𝛎𝟏 𝛏𝐞𝐪

nt = (n1 − ν1 ξeq ) + (n2 − ν2 ξeq ) + ν3 ξeq + ν4 ξeq

The partial pressure of various constituents can be written as
 (n1 − ν1 ξeq ) (n2 − ν2 ξeq ) ν3 ξeq ν4 ξeq
PA1 = Pt , PA2 = Pt , PA3 = Pt , PA4 = P
nt nt nt nt t

ν3 ν4 ν3 ν4
(PA3 ) × (PA4 ) (ν3 ξeq ) × (ν4 ξeq )Pt ∆υg
KP = ν1 ν2 = ν1 ν2 ( ) … … (1)
(PA1 ) × (PA2 ) (n1 − ν1 ξeq ) × (n2 − ν2 ξeq ) nt

If n amount of inert basis added to the system at equilibrium, the new extent of the reaction is
represented asξ′eq and nt be represented as n′t .

n′t = n + (n1 − ν1 ξ′eq ) + (n2 − ν2 ξ′eq ) + ν3 ξ′eq + ν4 ξ′eq

Here, n′t > nt , Then the new equilibrium constant,

ν3 ν4 ν3 ν4 ∆υg
(PA3 ) × (PA4 ) (ν3 ξ′eq ) × (ν4 ξ′eq ) Pt′
KP = ν1 ν2 = ν1 ν2 ( ) … … (2)
(PA1 ) × (PA2 ) (n1 − ν1 ξ′eq ) × (n2 − ν2 ξ′eq ) n′t

Case-1: If ∆υg = 0 from equation (1) and (2) we can write,ξeq = ξ′eq . Hence we can write that,
there is no effect on the equilibrium position by the addition of an inert gas

Case-2:

If ∆υg > 0 If ∆υg < 0

If inert gas is added at constant P, in this case If inert gas is added at constant P, in this case
denominator of equation (2) is greater than denominator of equation (2) is less than
equation (1). In order to keep K P constant, ξ′eq > equation (1). In order to keep K P constant, ξ′eq <
ξeq ξeq

Case-3:
If ∆𝛖𝐠 > 0 If ∆𝛖𝐠 < 0

If inert gas is added at constant V, If inert gas is added at constant V,

Considering ideal gas equation Pt V = nt RT, Considering ideal gas equation Pt V = nt RT,
Pt RT Pt′ Pt RT Pt′
= (before addition), ′ = (before addition), ′
nt V nt nt V nt
RT RT
= (after addition) = (after addition)
V V
∆υ ∆υ
Pt ∆υg RT ∆υg Pt′ g Pt ∆υg RT ∆υg Pt′ g
( ) =( ) = ( ′) ( ) =( ) = ( ′)
nt V nt nt V nt
 Substituting the value in equation (1) and (2) it Substituting the value in equation (1) and (2) it
is evident that at constant volume, ξeq = ξeq , that is evident that at constant volume, ξ′eq = ξeq , that
′

is there is no effect on equilibrium is there is no effect on equilibrium

Q. A mixture is composed of A and B in molar ratio 1:0.3, for a change of −𝟏𝟎𝐉 𝐦𝐨𝐥𝐞−𝟏 of
chemical potential of A what would be the change of B? 2015
Using Gibbs Duhem equation for binary mixture
nA 1
nA dμA + nB dμB = 0 or, dμB = − dμA = − × (−10 𝐉 𝐦𝐨𝐥𝐞−𝟏 ) = +33.3𝐉 𝐦𝐨𝐥𝐞−𝟏
nB 0.3

Hence the chemical potential of B increases by 33.3J mole−1

Q. For a reaction 𝟐𝐒𝐎𝟐 (𝐠) + 𝐎𝟐 (𝐠) ⇌ 𝟐𝐒𝐎𝟑 (𝐠), 𝐊 𝐏 = 𝟏𝟎 at 960K, for a reaction mixture
partial pressures 𝐩(𝐒𝐎𝟐 ) = 𝟏𝟎−𝟑 𝐛𝐚𝐫, 𝐩(𝐎𝟐 ) = 𝟎. 𝟎𝟐𝐛𝐚𝐫, 𝐩(𝐒𝐎𝟑 ) = 𝟏𝟎−𝟒 𝐛𝐚𝐫. Determine in
which direction reaction would be spontaneous?

2SO2 (g) + O2 (g) ⇌ 2SO3 (g)

p2SO3 (10−4 )2 1
QP = 2 = −3 2
=
pSO2 × pO2 (10 ) × 0.02 2
Q 1 1
Now, P⁄K = =
P 2 × 10 20
Reaction spontaneity is measured by
̅ = +RT ln (QP⁄ ) = +RT ln(1⁄ ) = (−)ve
∆G KP 20
So the reaction would be spontaneous
Q. For the reaction, 𝟐𝐊(𝐠) ⇌ 𝐊 𝟐 (𝐠), Derive the relation of 𝐊 𝐏 with 𝛏𝐞𝐪 and P 2012

2K(g) ⇌ K 2 (g)
t=0 2 0
t=t 2 − 2ξeq ξeq
Total mole nT = (2 − 2ξeq ) + ξeq = 2 − ξeq
Mole fraction 2 − 2ξeq ξeq
( ) ( )
nT nT
Partial 2 − 2ξeq ξeq
( )P ( )P
pressure nT nT
Now,
ξeq
p K2 ( n P) ξeq nT ξeq (2 − ξeq )
T
KP = = 2 = 2× P = 2
p2K 2 − 2ξeq 4(1 − ξeq ) 4(1 − ξeq ) P
( n P)
T
Q. 𝐇𝟐 𝐎(𝐥) ⇌ 𝐇𝟐 𝐎(𝐯), Depict chemical potential of 𝐇𝟐 𝐎 against T at constant P in the
vicinity of boiling point 2015

From the fundamental equation of pure water,

∂μ∗𝐇𝟐 𝐎
( ) = −S̅𝐇∗ 𝟐 𝐎
∂T P

Since absolute molar entropy is (+)ve always. So the slope of μ∗𝐇𝟐 𝐎 vs T will be (−)ve

(S̅𝐇∗ 𝟐 𝐎 ) > (S̅𝐇∗ 𝟐 𝐎 )

vap liq

Q. For a particular gas phase reaction 𝐊 𝐏 values were measured at different

temperatures (T). A plot of 𝐥𝐧 𝐊 𝐏 vs 𝟏⁄𝐓 gives a straight line with slope of 𝟏𝟎𝟑 𝐊. Mention
the condition that supports such a plot. Calculate ∆𝐫 𝐇 𝟎

From Vant-hoff isobar we can write,

∂ ln K P ∆r H 0 ∆r H 0 dT ∆r H 0 1
( ) = or, dlnK P = = − d( )
∂T P RT 2 R T2 R T
0
dlnK P ∆r H
=−
1 R
d (T)
∆ H0
Hence the slope of ln K P vs 1⁄T will be depends on − rR
 According to the given problem,
0
∆r H
− = 103 K or, ∆r H 0 = −8.314JK −1 mole−1 × 103 K = 8314 Jmole−1
R
Q. If the standard free energy of a reaction is positive, can the reaction proceed in
forward reaction? Explain your answer. 2011
Q. Analyze whether a reaction may be spontaneous in a direction with positive ∆𝐆𝟎
2012

The reaction spontaneity is measured by the term ∆G ̅ not by ∆G

̅ 0 , from vant Hoff reaction
Q
̅ = ∆G
∆G ̅ 0 + RT ln QP = −RT ln K P + RT ln QP = RT ln P
KP
At a constant T, K P always fixed, So, ∆G̅ always fixed. Now QP is defined by
0

P νB
∏B(Pdt) ( B )
P0
P νB
∏B(React) ( B )
P0
At the start of the reaction,
PB νB PB νB
∏ ( ) < ∏ ( ) and QP < 1
P0 P0
B(Pdt) B(React)
̅ = (−)ve
At that condition, QP < K P so, ∆G
̅ 0 , we cannot conclude anything from it. So, the statement
Hence whatever be the value of ∆G
̅ 0 means thermodynamically impossibility is not justified.
∆G

Q. Draw the free energy versus extent of the plot (ξ) plot A(g) ⇌ B(g). What will be the
nature of the plot if we assume that no mixing of reactant and product 2013

A(g) ⇌ B(g)

t=0 1 0
 t=t 1−ξ ξ

Gpure = (1 − ξ)μ∗A + ξ μ∗B = μ∗A + (μ∗B − μ∗A )ξ

So Gpure vs ξ will be a straight line. If ξ = 0, Gpure = μ∗A and when ξ = 1, Gpure = μ∗B
We know that,
G = Gpure + Gmix
∂G ∂G ∂G
̅ = ( ) = ( pure ) + ( mix )
∆r G
∂ξ T,P ∂ξ T,P ∂ξ T,P
At equilibrium, G in minimum
∂G
̅=(
∆r G ) =0
∂ξ T,P
∂Gpure ∂Gmix
therefore ( ) = −( ) (fig − 1)
∂ξ T,P ∂ξ T,P
If there will be no mixing then G = Gpure = μ∗A + (μ∗B − μ∗A )ξ no minimum in the plot is observed
∂G ∂Gpure
( ) =( ) (fig − 2)
∂ξ T,P ∂ξ T,P

𝟏 𝟑
Q. For the reaction 𝟐 𝐍𝟐 + 𝟐 𝐇𝟐 ⇌ 𝐍𝐇𝟑 at 298K, plot ∆𝐆 vs extent of the reaction ξ from ξ =0
to ξ =1. Also plot the affinity of the reaction vs ξ 2016
 𝟏 + 𝟑 ⇌ 𝐍𝐇𝟑 (g)
𝐍 𝐇
𝟐 𝟐 𝟐 𝟐

t=0 𝟏 𝟑 0
𝟐 𝟐
t=t 𝟏 𝟏 𝟑 𝟑 ξ
− 𝛏 − ξ
𝟐 𝟐 𝟐 𝟐

𝟏 𝟏 𝟑 𝟑 𝟏 𝟑 𝟏 𝟑
Gpure = ( − 𝛏) μ∗𝐍𝟐 + ( − 𝛏) μ∗𝐇𝟐 + ξ μ∗𝐍𝐇𝟑 = ( μ∗𝐍𝟐 + μ∗𝐇𝟐 ) + (μ∗𝐍𝐇𝟑 − μ∗𝐍𝟐 − μ∗𝐇𝟐 ) ξ
𝟐 𝟐 𝟐 𝟐 𝟐 𝟐 𝟐 𝟐
𝟏 ∗ 𝟑 ∗
So Gpure vs ξ will be a straight line. If ξ = 0, Gpure = (𝟐 μ𝐍𝟐 + 𝟐 μ𝐇𝟐 ) and when ξ = 1, Gpure =
μ∗𝐍𝐇𝟑
Since here ammonia is formed so heat is released by the system, hence the process is
exothermic in nature. Again we know that,
G = Gpure + Gmix
∂G ∂G ∂G
̅ = ( ) = ( pure ) + ( mix )
∆r G
∂ξ T,P ∂ξ T,P ∂ξ T,P
At equilibrium, G in minimum
∂G
̅=(
∆r G ) =0
∂ξ T,P
∂Gpure ∂Gmix
therefore ( ) = −( )
∂ξ T,P ∂ξ T,P
Q. What is the effect of introducing of neon gas into the system of equilibrium
𝐍𝟐 (𝐠) + 𝟑𝐇𝟐 (𝐠) ⇌ 𝟐𝐍𝐇𝟑 (𝐠)
At constant temperature and pressure 2018

𝐍𝟐 (𝐠) + 𝟑𝐇𝟐 (𝐠) ⇌ 𝟐𝐍𝐇𝟑 (𝐠)

1 3 0

1−ξ 3 − 3ξ 2ξ
2
2ξ
2
P𝐍𝐇 (n PT ) 4ξ2 nT 2
𝟑 T
KP = = = ( )
P𝐍𝟐 P𝐇3𝟐 1−ξ 3 − 3ξ 3 27(1 − ξ)4 PT
( n PT ) ( n PT )
T T
For low conversion, (1 − ξ) ≈ 1
4 2 nT 2
KP = ξ ( )
27 PT
When some amount of neon gas is added total amount of it is increases, 𝐧′𝐓 > nT
At a fixed temperature K P remains fixed, if it is added at constant pressure that means, PT
remains fixed
2
4 ′ 2 𝐧′𝐓
KP = ξ ( )
27 PT
In order to make constancy of K P , ξ < ξ. Hence the reaction will proceed in backward direction
′

after addition of inert gas at constant P.

Q. For the ideal gas reaction 𝐏𝐂𝐥𝟓 (𝐠) ⇌ 𝐏𝐂𝐥𝟑 (𝐠) + 𝐂𝐥𝟐 (𝐠), state with reasons, how the
equilibrium is affected when each of the following changes is made in the above
equilibrium is affected when each of the following changes is made in the equilibrium
mixture at 250C
(a) He(g) is added at constant T and P
(b) He(g) is added at constant T and V 2014

𝐏𝐂𝐥𝟓 (𝐠) ⇌ 𝐏𝐂𝐥𝟑 (𝐠) + 𝐂𝐥𝟐 (𝐠)

1 0 0
1−ξ ξ ξ
ξ ξ
P𝐏𝐂𝐥𝟑 P𝐂𝐥𝟐 (nT PT ) (nT PT ) ξ2 PT
KP = = = ( )
P𝐏𝐂𝐥𝟓 1−ξ (1 − ξ) nT
( n PT )
T
For low conversion, (1 − ξ) ≈ 1
PT
K P = ξ2 ( ) … (1)
nT
When some amount of inert gas is added total amount of it is increases, 𝐧′𝐓 > nT
′
2 𝐏𝐓
K P = ξ′ ( ′ ) … . . (2)
𝐧𝐓
Case 1: At a fixed temperature K P remains fixed, if inert gas is added at constant pressure that means, PT
remains fixed
2 PT
K P = ξ′ ( ′ )
𝐧𝐓
In order to make constancy of K P, ξ > ξ. Hence the reaction will proceed in forward direction
′

after addition of inert gas at constant P.

Case 2: At a fixed temperature K P remains fixed, if inert gas is added at constant volume, considering
ideal gas expression
Before addition of inert gas
PT RT
PT V = nT RT or, =
nT V
After addition of inert gas
𝐏𝐓′ RT
𝐏𝐓′ V = 𝐧′𝐓 RT or, ′ =
𝐧𝐓 V
So we can write,
𝐏𝐓′ PT
′ = at const T and V
𝐧𝐓 nT
In order to fixed K P, ξ′ = ξ, equilibrium remains unaltered.
Q. The standard Gibbs free energy of reaction for the decomposition of 𝐇𝟐 𝐎(𝐠) →
𝟏
𝐇𝟐 (𝐠) + 𝟐 𝐎𝟐 (𝐠) is 𝟏𝟏𝟖. 𝟎𝟖 𝐤𝐉𝐦𝐨𝐥𝐞−𝟏 at 2300K. What is the degree of dissociation of water
at 2300K and 1 bar?
2013

Given, ∆𝐺 0 = 118080 Jmole−1 from Vant Hoff isotherm

∆G0 = −RT ln K P
118080 Jmole−1 = −8.314Jk −1 mole−1 × 2300K × ln K P
K P = 2.08 × 10−3
Considering the reaction,

𝐇𝟐 𝐎(𝐠) ⇌ 𝑯𝟐 (𝒈) + 𝟏
𝑶 (𝒈)
𝟐 𝟐
1 0 0
1−𝜉 𝜉 𝜉⁄
2
𝜉 𝜉
Here total mole, 𝑛𝑇 = (1 − 𝜉) + 𝜉 + ⁄2 = (1 + ⁄2)
𝜉⁄
𝜉 𝑃 2 𝑃 (1 − 𝜉) 𝑃 𝑃
𝑝𝐻2 = ( ) 𝑝𝑂2 = ( ) 𝑝𝐻2 𝑂 = ( ) ℎ𝑒𝑟𝑒 =1
𝜉⁄ 𝑃 𝜉⁄ 𝑃 𝜉⁄
(1 + 2) 0 (1 + 2) 0 (1 + 2) 𝑃0 𝑃0

1⁄
ξ⁄ 2
ξ 2 }
×{ 1⁄
1⁄ ξ⁄ ξ ξ⁄ 2 ξ
pH (pO2 ) 2 (1 + 2) (1 + ⁄2) ξ (1 + ⁄2)
KP = 2 = = ×{ 2 } ×
p H2 O (1 − ξ) ξ⁄ ξ (1 − ξ)
(1 + 2) (1 + ⁄2)
ξ
(1 + ⁄2)
3⁄
ξ 2 1
= × 1⁄
√2(1 − ξ) ξ 2
(1 + ⁄2)
ξ
For very low conversion, (1 − ξ) ≈ 1 and (1 + ⁄2) ≈ 1
So the equation becomes,
3⁄
ξ 2
= 2.08 × 10−3 or, ξ = 0.02
√2

Q. The equilibrium constant of the reaction, 𝐀 𝟐 (𝐠) + 𝐁𝟐 (𝐠) ⇌ 𝟐𝐀𝐁(𝐠) at 1000C is 50. If 1
liter flask containing 1 mole of 𝐀 𝟐 is connected to a 2 liter flask containing 2 moles of 𝐁𝟐 ,
How many moles of AB will be formed at the said temperature 2009
2013 2019
Here ∆νg = 0
 KP = Kc

𝐀 𝟐 (𝐠) + 𝐁𝟐 (𝐠) ⇌ 𝟐𝐀𝐁(𝐠)

1 2 0
1−ξ 2−ξ 2ξ
Total volume at equilibrium = 2 + 1 = 3liter

1−ξ 2−ξ 2ξ
C𝐀𝟐 = ( ) C𝐁𝟐 = ( ) C𝐀𝐁 = ( )
3 3 3

2ξ 2
(C𝐀𝐁 )2 (3)
Kc = = = 50
C𝐀𝟐 C𝐁𝟐 1−ξ 2−ξ
( 3 )( 3 )

4ξ2 = 50(1 − ξ)(2 − ξ) or, 4ξ2 = 100 − 150ξ + 50ξ2 or, 46ξ2 − 150ξ + 100 = 0

150 ± √1502 − 400 × 46

ξ= so, ξ = 2.23 or 0.93
2 × 46
ξ = 2.23 is not acceptable here, so ξ = 0.93

Hence the number of moles of AB formed = 2 × 0.93 = 1.86 mole

Q. Prove that for an ideal gas reaction 2013

𝛛 𝐥𝐧 𝐊 𝐱 ∆𝐧
( ) =−
𝛛𝐏 𝐓 𝐏

We know that
K P = K x (P)∆n taking log on both sides ln K P = ln K x + ∆n ln P
Now differentiating with respect to P at constant T
∂ ln K P ∂ ln K x ∆n
( ) =( ) +
∂P T ∂P T P
Now the first term is zero. Since KP is independent of pressure,
∂ ln K P
( ) =0
∂P T
So the equation becomes,
∂ ln K x ∆n
( ) =−
∂P T P
Q. For the reaction
 𝐇𝟐 (𝐠) + 𝐈𝟐 (𝐠) ⇌ 𝟐𝐇𝐈(𝐠)
𝐊 𝐂 = 𝟓𝟎 𝐚𝐭 𝟒𝟒𝟖𝟎 𝐂 𝐚𝐧𝐝 𝐊 𝐂 = 𝟔𝟔. 𝟗 𝐚𝐭 𝟑𝟓𝟎𝟎 𝐂. 𝐅𝐢𝐧𝐝 ∆𝐄𝟎 𝐚𝐧𝐝 ∆𝐇 𝟎 𝐨𝐟 𝐭𝐡𝐞 𝐫𝐞𝐚𝐜𝐭𝐢𝐨𝐧 2004
Using the integrated form of Reaction Isochors
K 0c2 ∆E 0 1 1
ln 0 = [ − ]
K c1 R T1 T2
66.9 ∆E 0 1 1 −1
ln = [
−1 721K
− ] or, ∆E 0 = −11095.9 Jmole
50 −1 623K
8.314Jk mole
For the given reaction ∆νg = 2 − 1 − 1 = 0
From fundamental thermochemical reaction
−1
∆H 0 = ∆E 0 + ∆νg RT = ∆E 0 = −11095.9 Jmole
Q. Show that 2001 2013 2017
𝛛𝐆 𝛛𝐄 𝛛𝐆 𝛛𝐔
( ) =( ) 𝐨𝐫, ( ) =( )
𝛛𝐧𝐢 𝐓,𝐏,𝐧𝐣𝐬 𝛛𝐧𝐢 𝐒,𝐕,𝐧𝐣𝐬 𝛛𝐧𝐢 𝐓,𝐏,𝐧𝐣𝐬 𝛛𝐧𝐢 𝐒,𝐕,𝐧𝐣𝐬

For multi-component open system in terms of G

k
∂G
dG = −SdT + VdP + ∑ μi dni or, μi = ( )
∂ni T,P,n
i=1 js
j≠i

In terms of E
k
∂E
dE = TdS − PdV + ∑ μi dni or, μi = ( )
∂ni S,V,n
i=1 js
j≠i

Equating this two equation,

∂G ∂E
( ) =( )
∂ni T,P,n ∂ni S,V,n
js js
j≠i j≠i

Q. Calculate the vapor pressure of water at 500C. Given ∆𝐇 𝟎 = 𝟗𝟓𝟗𝟎 𝐜𝐚𝐥𝐦𝐨𝐥𝐞−𝟏 and ∆𝐒 𝟎 =
𝟐𝟔 𝐜𝐚𝐥𝐊 −𝟏 𝐦𝐨𝐥𝐞−𝟏 for the process 2001
From Gibbs Helmholtz equation
∆G = ∆H 0 − T∆S 0 = 9590 calmole−1 − 323K(26 calK −1 mole−1 ) = 1192 calmole−1
0

From vant hoff isotherm

∆G0 = −RT ln K P
1192 calmole−1 = −1.987 calK −1 mole−1 × 323K × ln K P
K P = 0.156
Here we consider the equilibrium, H2 O(l) ⇌ H2 O(vap)
PH O
K P = 2 = 0.156 or, PH2 O = 0.156atm
P0
Q. N2 and O2 combine at a given temperature to produce NO. At equilibrium the yield of
𝐊(𝐚+𝐛)
NO is 𝐱% by volume. If 𝐱 = √𝐊𝐚𝐛 − where K is the equilibrium constant of the
𝟒
reaction at the given temperature, where 𝐚 and b are the volume percentage of N2 and O2
in the initial pure mixture. What should be the initial composition of the reaction
mixture in order to maximum yield of NO ensured? 2013

Since a and b are the initial volume percentage of N2 and O2. Let us choose a basis of total
volume such that a + b = 100
So the given equation becomes,
100K
x = √Ka(100 − a) − = √Ka(100 − a) − 25K
4
Now differentiating the equation with respect to a
dx 1 1 K(100 − 2a)
= {Ka(100 − a)}− ⁄2 K(100 − 2a) =
da 2 2√Ka(100 − a)
For maximum yield,
dx
= 0 or, (100 − 2a) = 0 or, a = 50 so b = 100 − a = 50
da
Hence the initial mixture must contain 50 vol% of N2 and 50 vol% O2 to have maximum yield.

Q. Express 𝛍𝐢 of ZnCl2 in terms of 𝛍+ and 𝛍− . Express 𝐚𝐢 in terms of 𝐦𝐢 and 𝛄± 2012

ZnCl2 is a strong electrolyte,

𝐙𝐧𝐂𝐥𝟐 → 𝐙𝐧𝟐+ + 𝟐𝐂𝐥−

mi 0 0
0 mi 2mi

So, m+ = mi and m− = 2mi

a𝐙𝐧𝐂𝐥𝟐 = a𝐙𝐧𝟐+ × a2𝐂𝐥− = (C𝐙𝐧𝟐+ γ+ ) × (C𝐂𝐥− γ− )2 = (mi γ+ ) × (2mi γ− )2 = 4m3i (γ+ γ− 2 ) = 4m3i γ3±
μ𝐙𝐧𝐂𝐥𝟐 = μ𝐙𝐧𝟐+ + 2μ𝐂𝐥− = μ+ + 2μ−

Q. For a general chemical reaction at equilibrium prove tha 2015 2017

∆𝐇
𝛛𝛏 ∆𝐇
( ) = 𝐓⁄ 𝟐 =
𝛛𝐓 𝐏,𝐞𝐪 𝛛 𝐆
( 𝟐) 𝐓𝐆𝐞′′
𝛛𝛏 𝐞𝐪
All terms have their usual significance
From the definition of reaction potential,
∂G
∆G = ( ) … . (1)
∂ξ T,P
So it can be written that ∆G = f(T, P, ξ)
∂∆G ∂∆G ∂∆G
d∆G = ( ) dT + ( ) dP + ( ) dξ
∂T P,ξ ∂P T,ξ ∂ξ T,P
d∆G = −∆SdT + ∆VdP + G′′ dξ … . . (2)
Where,
′′
∂ ∂G ∂2 G
G ={ ( ) } = ( 2)
∂ξ ∂ξ T,P ∂ξ T,P
T,P
At equilibrium, d∆G = 0
Then the equation (2) becomes,
′′ (∂ξ)
−∆S(∂T)eq + ∆V(∂P)eq + Geq eq = 0 … … (3)
Applying Gibbs Helmholtz equation,
∆H
∆G = ∆H − T∆S, or, ∆S = (at equilibrium)
T
Putting the value in equation (3)
∆H ′′ (∂ξ)
− (∂T)eq + ∆V(∂P)eq + Geq eq = 0
T
Here in this equation, Geq
′′
is always a positive quantity.
At equilibrium constant Pressure,
∆H
∂ξ ∆H T
( ) = ′′ = ⁄∂2 G
∂T P,eq TGeq ( 2)
∂ξ eq

Q. Calculate 𝐊 𝐏 and ∆𝐆𝟎 for the following reaction at 200C,

𝐂𝐮𝐒𝐎𝟒 . 𝟒𝐍𝐇𝟑 (𝐬) ⇌ 𝐂𝐮𝐒𝐎𝟒 . 𝟐𝐍𝐇𝟑 (𝐬) + 𝟐𝐍𝐇𝟑 (𝐠)
The equilibrium pressure of 𝐍𝐇𝟑 is 62 mm of Hg 2007

P𝐍𝐇𝟑 2 62 mm of Hg 2
KP = ( ) =( ) = 0.00665
P0 760 mm of Hg

From the Vant-hoff isotherm

∆G0 = −RT ln K P == −8.314Jk −1 mole−1 × 2300K × ln 0.00665

Q. For the dissociation 𝐍𝟐 𝐎𝟒 (𝐠) ⇌ 𝟐𝐍𝐎𝟐 (𝐠), Show that

⁄𝟐 𝟏
𝐊𝐏
(𝐢)𝐊 𝐏 = 𝐊 𝐱 𝐏 (𝐢𝐢)𝛏𝐞𝐪 = ( )
𝐊 𝐏 + 𝟒𝐏
where 𝛏𝐞𝐪 is the extent of reaction at equilibrium 2017
Q. Consider the dissociation equilibrium 𝐍𝟐 𝐎𝟒 (𝐠) ⇌ 𝟐𝐍𝐎𝟐 (𝐠)
Assuming that we start with 1 mole of 𝐍𝟐 𝐎𝟒 (𝐠) and no 𝐍𝐎𝟐 (𝐠), show that the degree of
𝟏⁄
𝐊𝐏 𝟐
dissociation of 𝐍𝟐 𝐎𝟒 may be given as 𝛂 = (𝐊 ) . Check that your result is in accord
𝐏 +𝟒𝐏
with La Chatelier’s principle 2009

𝐍𝟐 𝐎𝟒 (𝐠) ⇌ 𝟐𝐍𝐎𝟐 (g)

t=0 1 0
t=t 1 − ξeq 2ξeq
Total mole 𝑛𝑇 = (1 − ξeq ) + 2ξeq = 1 + ξeq
Mole fraction 1 − ξeq 2ξeq
( ) ( )
1 + ξeq 1 + ξeq
Partial pressure 1 − ξeq 2ξeq
( )𝑃 ( )𝑃
1 + ξeq 1 + ξeq

2
2ξeq
p2𝐍𝐎𝟐 ( P)
1 + ξeq 4ξ2eq P 4ξ2eq P
KP = = = =
p𝐍𝟐 𝐎𝟒 1 − ξeq (1 − ξeq )(1 + ξeq ) (1 − ξ2eq )
( P)
1 + ξeq
K P − ξeq K P = 4ξeq P or, K P = ξ2eq K P + 4ξ2eq P or, K P = ξ2eq (K P + 4P)
2 2

KP
ξeq = √
(K P + 4P)
For the relation,
P ∆νg
KP = Kx ( ) In case of given reaction ∆νg = (2 − 1) = 1
1 atm
KP = KxP
Second part (2009): Here ξ is replaced by 𝛂 in derivation and arrive up to
4α2 P
KP =
(1 − α2 )
For low conversion (1 − α2 ) ≈ 1 so the equilibrium constant represented by
K P = 4α2 P
At fixed temperature, in order to maintain fixedK P , with the increase in pressure P, α decreases so the
reaction proceed to backward direction
𝛛𝛍 ̅𝐢 , where the terms have their usual significance.
Q. Show that ( 𝐢⁄𝛛𝐏) = 𝐕
𝐓,𝐍
2004 2008 2016 2019

From definition of chemical potential

∂G
μi = ( )
∂ni T,P,n
js
j≠i
Differentiating μi with respect to T, keeping P and njs constant

∂μi ∂ ∂G
( ) ={ ( ) }
∂P T,njs ∂P ∂ni T,P,n
js
j≠i T,njs
Since G is a state function,
∂μi ∂ ∂G ∂
( ) ={ ( ) } ={ (V)} ̅i
=V
∂P T,njs ∂ni ∂P T,njs ∂ni T,P,n
T,P,n js js
j≠i j≠i
𝛛𝐇
Q. Show that 𝛍𝐢 = (𝛛𝐧 ) 2015
𝐢 𝐒,𝐏,𝐧 𝐣𝐬
𝐣≠𝐢

For multicomponent system

k

dG = −SdT + VdP + ∑ μi dni

i=1

Again we can write that G = H − TS, or, dG = dH − TdS − SdT

Putting the value dG in the equation
k

−SdT + VdP + ∑ μi dni = dH − TdS − SdT

i=1
k

dH = TdS + VdP + ∑ μi dni

i=1

𝛛𝐇
𝛍𝐢 = ( )
𝛛𝐧𝐢 𝐒,𝐏,𝐧 𝐣𝐬
𝐣≠𝐢

Q. Derive the relationship

𝐝𝐥𝐧𝐊 𝐏 ∆𝐇 𝟎
=
𝐝𝐓 𝐑𝐓 𝟐
In the above relationship, ∆𝐇 is assumed to be constant. If this is not so and ∆𝐇 𝟎 can be
𝟎

expressed as a power series of T such as

∆𝐇 𝟎 = ∆𝐇𝟎𝟎 + 𝐀′ 𝐓 + 𝐁 ′ 𝐓 𝟐 + 𝐂 ′ 𝐓 𝟑 + ⋯
Obtain an expression for 𝐥𝐧 𝐊 𝐏 using the value of ∆𝐇 𝟎 2015
From the vant hoff isotherm,
∆G0 = −RT lnK P
Dividing with T
∆G0
= −R lnK P
T
Differentiating with respect to T keeping P constant
 d ∆G0 dlnK P
( ) = −R … . . (1)
dT T dT
From Gibbs Helmholtz equation,
d ∆G0 ∆H 0
( )=− 2
dT T T
Putting the value in equation (1)
dlnK P ∆H 0
−R =− 2
dT T
dlnK P ∆H 0
or, =
dT RT 2
Applying the given value
∆H 0 = ∆H00 + A′ T + B′ T 2 + C′ T 3 + ⋯ in the equation,

dlnK P (∆H00 + A′ T + B′ T 2 + C′ T 3 + ⋯ )
=
dT RT 2
dlnK P ∆H00 A′ B′ C′
= + + + T+⋯
dT RT 2 RT R R
∆H00 A′ B′ C′
dlnK P = dT + dT + dT + TdT + ⋯
RT 2 RT R R
∆H00 dT A′ dT B′ C′
∫ dlnK P = ∫ 2+ ∫ + ∫ dT + ∫ T dT + ⋯
R T R T R R
∆H00 A′ B′ C′ 2
lnK P = − + ln T + T + T +⋯
RT R R 2R
Q. The equilibrium constant 𝐊 𝐏 varies on temperature as
𝟏𝟎𝟖𝟖 𝟏. 𝟓𝟏 × 𝟏𝟎𝟓
𝐥𝐧 𝐊 𝐏 = −𝟏. 𝟎𝟒 − + 𝐢𝐧 𝟑𝟎𝟎𝐊 − 𝟔𝟎𝟎𝐊
𝐓 𝐓𝟐
Calculate ∆𝐒 𝟎 at 400K 2007
Putting 300K
1088 1.51 × 105
ln 𝐾𝑃,300𝐾 = −1.04 − + = −2.988
300 3002
Putting 600K
1088 1.51 × 105
ln 𝐾𝑃,600𝐾 = −1.04 − + = −2.433
600 6002
Subtracting this two equation,
ln 𝐾𝑃,600𝐾 − ln 𝐾𝑃,300𝐾 = −2.433 − (−2.988) = 0.554
𝐾𝑃,600𝐾
ln = 0.554
𝐾𝑃,300𝐾
From Vanthoff isobar,
 𝐾𝑃,600𝐾 ∆𝐻 0 1 1
ln = [ − ] = 0.554
𝐾𝑃,300𝐾 𝑅 300𝐾 600𝐾
600K × 300K
∆H 0 = 0.554 × × 8.314JK −1 mole−1 = 2764.12 Jmole−1
(600K − 300K)
Assuming ∆H 0 is fixed in the temperature range 300K-600K. So again using Vanthoff isobar in the
temperature range 300K to 400K
𝐾𝑃,400𝐾 ∆𝐻 0 1 1
ln = [ − ]
𝐾𝑃,300𝐾 𝑅 300𝐾 400𝐾
2764.12 Jmole−1 1 1
ln 𝐾𝑃,400𝐾 − ln 𝐾𝑃,300𝐾 = −1 −1
[ − ]
8.314JK mole 300𝐾 400𝐾
2764.12 Jmole−1 1 1
ln 𝐾𝑃,400𝐾 − (−2.988) = −1 −1
[ − ]
8.314JK mole 300𝐾 400𝐾
ln 𝐾𝑃,400𝐾 = −2.71 𝑜𝑟, 𝐾𝑃,400𝐾 = 0.066
Using Vanthoff isotherm at 400K
0
∆𝐺400𝐾 = −𝑅𝑇 ln 𝐾𝑃,400𝐾 = −8.314JK −1 mole−1 × 400K × (−2.71) = 9012.376 Jmole−1
According to assumption,
0 0 0
∆𝐻300𝐾 = ∆𝐻600𝐾 = ∆𝐻400𝐾
From Gibbs Helmholtz equation,
0 0 0 0
∆𝐺400𝐾 = ∆𝐻400𝐾 − 𝑇∆𝑆400𝐾 𝑜𝑟, 9012.376 Jmole−1 = 2764.12 Jmole−1 − (400K)∆𝑆400𝐾

𝐐. 𝟐𝐁𝐫𝐂𝐥(𝐠) ⇌ 𝐂𝐥𝟐 (𝐠) + 𝐁𝐫𝟐 (𝐠); 𝐊 𝐏𝟏 = 𝟎. 𝟏𝟔𝟗

𝟐𝐈𝐁𝐫(𝐠) ⇌ 𝐈𝟐 (𝐠) + 𝐁𝐫𝟐 (𝐠); 𝐊 𝐏𝟐 = 𝟎. 𝟎𝟏𝟒𝟗
At a certain temperature, determine 𝐊 𝐏 for the reaction at the same temperature
𝟏 𝟏
𝐁𝐫𝐂𝐥(𝐠) + 𝟐 𝐈𝟐 (𝐠) ⇌ 𝐈𝐁𝐫(𝐠) + 𝟐 𝐂𝐥𝟐 (𝐠) 2018
Constructing the given equation,
1 1 ∆G10⁄
BrCl(g) ⇌ Cl2 (g) + Br2 (g) 2
2 2
1 1 0
∆G
I (g) + Br2 (g) ⇌ IBr(g) − 2⁄2
2 2 2
1 1 ∆G10 − ∆G20
BrCl(g) + I2 (g) ⇌ IBr(g) + Cl2 (g) ∆GT0 =
2 2 2
2∆GT0 = ∆G10 − ∆G20 or, −2RT lnK P = −RT lnK P1 + RT lnK P2
K K 0.169
or, −2 lnK P = − lnK P1 + lnK P2 or, − ln(K P )2 = − ln KP1 or, K P = √KP1 = √0.0149
P2 P2

Q. ∆𝐆𝟎 values for hydrolysis of 𝐆𝐥𝐮𝐜𝐨𝐬𝐞 − 𝟏 − 𝐩𝐡𝐨𝐬𝐩𝐡𝐚𝐭𝐞 and Glucose-6-phosphate are

−𝟐𝟏𝐤𝐉𝐦𝐨𝐥𝐞−𝟏 and −𝟏𝟒𝐤𝐉𝐦𝐨𝐥𝐞−𝟏 . Calculate the equilibrium constant of the following
equilibrium at 250C
𝐆𝐥𝐮𝐜𝐨𝐬𝐞 − 𝟏 − 𝐩𝐡𝐨𝐬𝐩𝐡𝐚𝐭𝐞 ⇌ 𝐆𝐥𝐮𝐜𝐨𝐬𝐞 − 𝟔 − 𝐩𝐡𝐨𝐬𝐩𝐡𝐚𝐭𝐞 2012
 According to the given problem,
Glucose − 1 − phosphate + H2 O ⇌ Glucose − hydrate + (PO3−
4 )part ∆G10 = −21kJmole−1
Glucose − 6 − phosphate + H2 O ⇌ Glucose − hydrate + (PO3−
4 )part ∆G20 = −14kJmole−1
Rearranging the equation
Glucose − 1 − phosphate + H2 O ⇌ Glucose − hydrate + (PO3−
4 )part ∆G10 = −21kJmole−1
0
Glucose − hydrate + (PO3−4 )part ⇌ Glucose − 6 − phosphate + H2 O ∆G2 = +14kJmole
−1
0 −1
Glucose − 1 − phosphate ⇌ Glucose − 6 − phosphate ∆G = −7kJmole
From vanthoff isotherm,
∆G0 = −RT ln K P = −7000 Jmole−1
−8.314JK −1 mole−1 × 298K × ln K P = −7000 Jmole−1 or, K P =

Q. At 929K, the total gas pressure is 0.98 atm. For the reaction
𝟐𝐅𝐞𝐒𝐎𝟒 (𝐬) ⇌ 𝐅𝐞𝟐 𝐎𝟑 (𝐬) + 𝐒𝐎𝟐 (𝐠) + 𝐒𝐎𝟑 (𝐠)
(i) Calculate 𝐊 𝐏
(ii) What will be the total equilibrium pressure if excess 𝐅𝐞𝐒𝐎𝟒 is placed in a flask at
929K containing 𝐒𝐎𝟐 at 0.4 atm. 2009
From the stoichiometry,
p𝐒𝐎𝟐 = p𝐒𝐎𝟑 = p
𝑝𝑇 = p𝐒𝐎𝟐 + p𝐒𝐎𝟑 = p + p = 2p = 0.98 atm or, p = 0.49 atm
p𝐒𝐎 p𝐒𝐎 p p p 2 0.49 atm 2
KP = ( 𝟐 ) ( 𝟑 ) = ( ) ( ) = ( ) = ( ) = (0.49)2
p0 p0 p0 p0 p0 1 atm
Now the reaction is started with some 𝐒𝐎𝟐 𝐨𝐟 𝟎. 𝟒 𝐚𝐭𝐦 𝐩𝐫𝐞𝐬𝐬𝐮𝐫𝐞. 𝐀𝐭 this new condition let us
assume
p𝐒𝐎𝟐 = p𝐒𝐎𝟑 = p′ (from reaction)
The new pressure of the constituents,
p′𝐒𝐎𝟐 = (p′ + 0.4) atm where 0.4 atm is stands for outside addition of 𝐒𝐎𝟐
p′𝐒𝐎𝟑 = p′
As the temperature remains same K P also be same
p′𝐒𝐎𝟐 p′𝐒𝐎𝟑 p′ + 0.4 p′ p′ (p′ + 0.4)
KP = ( )( )=( )( ) = = (0.49)2
p0 p0 p0 p0 1
p′ = 0.329
Hence the total pressure of the system
𝑃𝑇′ = p′𝐒𝐎𝟑 + p′𝐒𝐎𝟐 = p′ + p′ + 0.4 = 2p′ + 0.4 = 1.058 atm

Define fugacity and fugacity coefficient

For infinitesimally small change in T and P, the free energy of the system can be written as,
dG = −SdT + VdP
At constant T,
dG = +VdP
G2 P2
nRT
∫ dG = ∫ dP (considering ideal gas equation)
P
G1 P1
After integration,
P2 P2
G2 − G1 = nRT ln or, μ2 − μ1 = RT ln (only applicable for ideal gas)
P1 P1
This equation depends upon the nature of the gas (here only for ideal gas). G.N. Lewis incorporates an
alternate approach to represent the above equation which is independent upon the nature or behavior
of the gas. The main backbone of the equation remains unaltered by introducing a function ′f′ which is
called fugacity, of a real gas denoted by the following way:
𝐟𝟐 𝐟𝟐
𝐆𝟐 − 𝐆𝟏 = 𝐧𝐑𝐓 𝐥𝐧 𝐨𝐫, 𝛍𝟐 − 𝛍𝟏 = 𝐑𝐓 𝐥𝐧
𝐟𝟏 𝐟𝟏
Fugacity coefficient: Fugacity coefficient, which plays a relation between fugacity and pressure
such that
𝐟
=𝚼
𝐏
Where, Υ be the fugacity coefficient which accounts the deviation of a real gas from ideality. When P → 0.
i.e., all the real gas approach to ideality, we can write
f
lim = lim Υ = 1
P→0 P P→0
fi
For multi component, P → Υi
i

Q. Justify the statement that the fugacity coefficient is the main parameter which deviates the
real gas from ideality
The chemical potential of a real gas ‘i’ in a mixture at fugacity fi relative to standard fugacity f0 can be
writtenas,
fi
μi (T, fi ) = μ0i (T) + RT ln , where f0 be the standard fugacity
f0
Υi Pi
μi (T, fi ) = μ0i (T) + RT ln
f0
Pi
μi (T, fi ) = μ0i (T) + RT ln + RT ln Υi
f0
When, P → 0, f0 → P0
Pi
μi (T, fi ) = μ0i (T) + RT ln + RT ln Υi
P0
μi (T, fi ) = μi (T, Pi ) + RT ln Υi
It can be said that the deviation of a real gas in a mixture from ideality in a mixture from ideality in a
mixture depends on Υi , where μ0i is the characteristics of an of an ideal gas, hence the main parameter
which deviates the real gas from ideality by Υi
Q. Prove that,
𝐏
𝐟𝟐 𝐙−𝟏
𝐥𝐧 = ∫ 𝐝𝐏, where Z is the compressibility factor
𝐏𝟐 𝐏
𝟎
From definition,
P2 P2
P2 f2
∫ Vm,ideal dP = μ2,id − μ1,id = RT ln … . (1) ∫ Vm,real dP = μ2,real − μ1,real = RT ln … . (2)
P1 f1
P1 P1
Subtracting (1) from (2)
P2
f2 P1
∫ (Vm,real − Vm,ideal ) dP = RT ln ( × )
P2 f1
P1
If P1 be allowed to approach zero value,
f1
lim →1
P1 →0 P1
P2 P2
f2 Vm,real f2
∫ (Vm,real − Vm,ideal ) dP = RT ln or, ∫ Vm,ideal ( − 1) dP = RT ln
P2 Vm,ideal P2
0 0
P2
f2 Vm,ideal Vm,real
ln =∫ ( − 1) dP
P2 RT Vm,ideal
0
P2
f2 (Z − 1)
ln = ∫ dP
P2 P
0

Q. Neglecting the pressure correcting term of Vander Waal gas, prove that,
𝐟 𝐛𝐏
𝐥𝐧 =
𝐏 𝐑𝐓
Also show that the pressure of a gas is the geometric mean of ideal pressure and fugacity
Considering 1 mole of Vander Waal gas,
a
(P + 2 ) (vm − b) = RT
vm
Neglecting the pressure correction factor, we can write, P(vm − b) = RT or, Pvm = RT + bP
RT Pvm Pb Pb
P= or, − = 1 or, Z − 1 = … … . (1)
(vm − b) RT RT RT
We can write that,
P
f (Z − 1)
ln = ∫ dP
P P
0
Putting the value from (1)
 P
f b bP f bP
ln = ∫ dP = or, = exp ( )
P RT RT P RT
0
f bP bP 2 1
or, =1+( )+( ) +⋯
P RT RT 2!
Neglecting the higher term,
f bP RT + bP Pvm P
=1+( )= = =Z=
P RT RT RT Pid
2
P = f × Pid
̅ − 𝐛) = 𝐑𝐓
Q. Derive the expression of fugacity coefficient of a gas obeying the equation 𝐏(𝐕
2017

From fundamental equation,

P
f (Z − 1)
ln = ∫ dP … . . (1)
P P
0
Using the given equation, P(V̅ − b) = RT or, PV
̅ = RT + bP
̅
PV bP Z−1 b
Z= =1+ or, =
RT RT P RT
Putting the value in equation (1)
P P
f (Z − 1) b bP
ln = ∫ dP = ∫ dP =
P P RT RT
0 0
bP
γ= e
RT

Q. An approximate equation of state for H2 gas at 250C is 𝐏(𝐕 − 𝐛) = 𝐑𝐓 for 1 mole of the
gas, the value of b is 𝟐. 𝟔𝟕 × 𝟏𝟎−𝟓 𝐦𝟑 𝐦𝐨𝐥𝐞−𝟏 ; when P is in Nm-2. Use this information to
evaluate the fugacity at 250C and 50 atm 2016

From fundamental equation,

P
f (Z − 1)
ln = ∫ dP … . . (1)
P P
0
Using the given equation, P(V − b) = RT or, PV = RT + bP
PV bP Z−1 b
Z= =1+ or, =
RT RT P RT
Putting the value in equation (1)
P P
f (Z − 1) b bP
ln = ∫ dP = ∫ dP =
P P RT RT
0 0
bP
f = P exp ( )
RT
−𝟓 −𝟏
bP 𝟐. 𝟔𝟕 × 𝟏𝟎 𝐦𝟑 𝐦𝐨𝐥𝐞 × 𝟓𝟎 × 𝟏𝟎𝟏𝟑𝟐𝟓𝐍𝐦−𝟐
f = P exp ( ) = 50atm × exp ( )
RT 8.314JK−1 mole−1 × 298K
Q. The fugacity coefficient of a certain gas at 200K and 50 bar is 0.72. Calculate the difference of
its chemical potential from that of a perfect gas in the same state. 2012 2014

The difference in chemical potential of a real gas compared to that of an ideal gas is represented as
μi (T, fi ) = μi (T, Pi ) + RT ln Υi
Where Υi is the fugacity coefficient. The change in chemical potential
∆μi = RT ln Υi = 8.314JK −1 mole−1 × 298K ln 0.72

Q. 𝟐𝐀 + 𝐁 ⇌ 𝟑𝐂 + 𝟐𝐃; it was found that when one mole A, 2 mole of B, 1 mole of D were
mixed and the resulting mixture contain 0.9 mole C, at a total pressure 1 bar, calculate
the mole fraction of each species at equilibrium and ∆𝐆𝟎 2011

𝟐𝐀 + 𝐁 ⇌ 𝟑𝐂 + 𝟐𝐃
𝐭=𝟎 1 2 0 1
𝐭=𝐭 1 − 2ξ 2−ξ 3ξ 1 + 2ξ
Here PT = 1 bar also P0 = 1bar, now according to the given problem,
3ξ = 0.9 mole or, ξ = 0.3 mole
Total mole nT = 1 − 2ξ + 2 − ξ + 3ξ + 1 + 2ξ = 4 + 2ξ = (4 + 2 × 0.3)mole = 4.6 mole
1 − 2ξ (1 − 2 × 0.3) 0.4 2−ξ (2 − 0.3) 1.7
xA = = = xB = = =
4 + 2ξ (4 + 2 × 0.3) 4.6 4 + 2ξ (4 + 2 × 0.3) 4.6
3ξ (3 × 0.3) 0.9 1 + 2ξ (1 + 2 × 0.3) 1.6
xC = = = xD = = =
4 + 2ξ (4 + 2 × 0.3) 4.6 4 + 2ξ (4 + 2 × 0.3) 4.6
Now,
0.9 3 1.6 2
PC3 PD2 (xC P)3 (xD P)2 (xC )3 (xD )2 (4.6) (4.6)
KP = 2 = = =
PA PB (xA P)2 (xB P) (xA )2 (xB ) 0.4 2 1.7
(4.6) (4.6)
From vant hoff isotherm,
3 2
0.9 1.6
( ) ( )
∆𝐆𝟎 = −𝐑𝐓 𝐥𝐧K P = −8.314 JK−1 mole−1 × 298K 𝐥𝐧 4.6 2 4.6
0.4 1.7
(4.6) (4.6)

Q. 1 gm mole of gas PQ dissociate to an extent of 10% at 127 0C, occupies a volume of 40

lit, (i) calculate the total pressure at this temperature (ii) 𝐊 𝐏 for the reaction. 𝐊 𝐏 is found
to increase with temperature, show that the reaction must be endothermic
2011

PQ → P + Q
1 0 0
1−ξ ξ ξ
Total mole nT = 1 + ξ
Assuming ideal behavior at equilibrium,
 nT (1 + ξ)
PV = nT RT or, P = RT or, P = RT
V V
10
(1 + ξ) (1 + 100) mole × 0.0821litatmK −1 mole−1
P= RT = = 0.9031atm
V 40 lit
ξ ξ
CP CQ ( ⁄V) ( ⁄V) ξ2 0.12
KC = = = = = 2.7 × 10−4
CPQ 1−ξ (1 − ξ)V (1 − 0.1)40
( V )
For the reaction, ∆νg = 1
C0 RT ∆νg C0 RT 1 moleliter −1 × 0.0821litatmK −1 mole−1 × 400K
KP = KC ( ) = KC ( ) = 2.7 × 10−4 ( )
P0 P0 1 atm
= 8.86 × 10−3
From the differential form of isobar
dlnK P ∆H 0 1 dK P ∆H 0
= or, =
dT RT 2 K P dT RT 2
dKP
According to the given problem, dT
= (+)ve. So, ∆H 0 = (+)ve. Which is applicable for endothermic
reaction
Q. Define mean ionic activity coefficient of ions with respect to a solution of a binary
electrolyte 𝐀 𝐱 𝐁𝐲 in water (𝛖𝐀 𝐚𝐧𝐝 𝛖𝐁 𝐚𝐫𝐞 𝐭𝐡𝐞 𝐫𝐞𝐬𝐩𝐞𝐜𝐭𝐢𝐯𝐞 𝐯𝐚𝐥𝐞𝐧𝐜𝐢𝐞𝐬) 2011

Ax By → xAy+ + yBx−
According to the given problem x = υA and y = υB , then we can write the equation as
Ax By → υA AυB + + υB BυA −
υ +υB υ υ
γ±A = γAAυB+ γBBυA −
1⁄
υ υ (υA +υB )
γ± = (γAAυB+ γBBυA − )
𝐝 𝐥𝐧 𝐊 𝐜 ∆𝐔 𝟎
Q. Show that = 𝐑𝐓𝟐 , for a reaction involving ideal gases 2014
𝐝𝐓

From the dependence of K P and K C , we can write,

c0 RT ∆υg 1mole
KP = KC ( ) assuming c0 = , P0 = 1 atm
P0 lit
K P = K C (RT)∆υg , ln K P = ln K C + ∆υg ln RT = ln K C + ∆υg ln R + ∆υg ln T
Differentiating with respect to T, we can write,
dlnK P dlnK C ∆υg
= +
dT dT T
Using reaction isobar we can write,
∆H 0 dlnK C ∆υg dlnK C ∆H 0 ∆υg
= + or, = −
RT 2 dT T dT RT 2 T
0
dlnK C ∆H − ∆υg RT
= … … (1)
dT RT 2
From the thermo chemical equation,∆H 0 = ∆U 0 + ∆υg RT
Using this equation in equation (1)
dlnK C ∆U 0
=
dT RT 2
Q. For a particular gas phase reaction 𝐊 𝐏 values were measured at different temperatures (T).
A plot of 𝐥𝐧 𝐊 𝐏 vs 𝟏⁄𝐓 gives a straight line with slope of 𝟏𝟎𝟑 𝐊. Mention the condition that supports
such a plot. Calculate ∆𝐫 𝐇 𝟎

From Vant-hoff isobar we can write,

∂ ln K P ∆r H 0 ∆r H 0 dT ∆r H 0 1
( ) = or, dlnK P = =− d( )
∂T P RT 2 R T2 R T
dlnK P ∆r H 0
=−
1 R
d (T)
∆ H0
Hence the slope of ln K P vs 1⁄T will be depends on − rR

According to the given problem,

0
∆r H
− = 103 K or, ∆r H 0 = −8.314JK −1 mole−1 × 103 K = 8314 Jmole−1
R
𝐊𝐏
Q. The relation 𝐊 𝐏 = 𝐊 𝐂 (𝐑𝐓) for𝐍𝟐 𝐎𝟒 (𝐠) ⇌ 𝟐𝐍𝐎𝟐 (𝐠) implies that ⁄𝐊 has the SI unit
𝐂
𝐉𝐦𝐨𝐥𝐞−𝟏 − − − 𝐣𝐮𝐬𝐭𝐢𝐟𝐲 𝐨𝐫 𝐜𝐫𝐢𝐭𝐢𝐜𝐢𝐳𝐞 2015

From the given reaction,

N2 O4 (g) ⇌ 2NO2 (g)
∆νg = 2 − 1 = 1
According to the given problem,
KP
K P = K C (RT) or, = (RT) = JK −1 mole−1 × K = Jmole−1
KC
But this is not true relation. With respect to standard one,
 C0 RT ∆νg C0 RT KP C0 RT
KP = KC ( ) = KC ( ) or, =( )
P0 P0 KC P0
Using the unit of each term,
KP C0 RT moleliter−1 × litatmK−1 mole−1 × K
=( )=( ) = unitless
KC P0 atm
Hence the given statement is not justified.

Q. Fugacity 𝐟𝐢 plays the same role in a non ideal gas mixture as the partial pressure 𝐩𝐢 in
an ideal gas mixture-----justify 2018
The chemical potential of a non ideal gas ‘i’ in a mixture at fugacity fi relative to standard fugacity f0 can be
written as,
fi
μi (T, fi ) = μ0i (T) + RT ln , where f0 be the standard fugacity (1)
f0
On the other hand The chemical potential of a ideal gas ‘i’ in a mixture at partial pressure pi relative to
standard pressure p0 can be written as,
pi
μi (T, pi ) = μ0i (T) + RT ln , where p0 be the standard pressure (2)
p0
The nature of the two equations (1) and (2) are same but the difference is that
Υi Pi
μi (T, fi ) = μ0i (T) + RT ln
f0
Pi
μi (T, fi ) = μ0i (T) + RT ln + RT ln Υi
f0
When, P → 0, f0 → P0
Pi
μi (T, fi ) = μ0i (T) + RT ln + RT ln Υi
P0
μi (T, fi ) = μi (T, Pi ) + RT ln Υi
It can be said that the deviation of a real gas in a mixture from ideality in a mixture from ideality in a
mixture depends on Υi , where μi (T, Pi ) is the characteristics of an of an ideal gas, hence the main
parameter which deviates the real gas from ideality by Υi .

Q. Chemical potential 𝛍 and standard chemical potential 𝛍𝟎 of a real gas is represented as

𝛍 = 𝛍𝟎 + 𝐑𝐓𝐥𝐧 𝐟. Comment on the pressure and temperature dependence of 𝛍 and 𝛍𝟎
2010
The chemical potential of a real gas at fugacity f relative to standard chemical potential can be written as,
f
μ(T, f) = μ0 (T) + RT ln
1atm
Where μ(T, f)the formal chemical potential of real gas which is is depends on fugacity of that
constituents as well as temperature T and μ0 is the standard chemical potential depends only
on T
Q. The volume (in ml) of NaCl solution, per 1000 gm of water at 250C is given by
𝐕 = 𝟏𝟎𝟎𝟐. 𝟗 + 𝟏𝟔. 𝟒𝟎𝐦 + 𝟐. 𝟓𝐦𝟐
where m is the concentration in molality, Derive the general expression for the partial molar
volume of sodium chloride in a aqueous solution
2016
Molality m means 1000 gm solvent contains m mole of solute, Here also the solvent amount will be 1000
gm so the molality here is equal to the mole of solute
∂V
VNaCl,pm = ( ) = 16.4 + 5m
∂m T,P,nH2O
Q. Elucidate the concept of chemical potential (𝛍) as escaping tendency and mention its
significance with respect to equilibrium state of a system. 2001 2009 2013

Suppose a substance is present in different phase α and β. So the chemical potential of that substance is
same, if the substance be in equilibrium. We can write that, μα = μβ
If dn be the amount of substance transfer from αto β. So the two equations becomes,
dGα = μα (−dn)and, dG β = μβ (dn)
So the total change in free energy of the system, dG = dGα + dG β = (μβ − μα )dn
If μα > μβ , dn = (+)ve, dG = (−)ve Then the above transfer of substance from α to β occur
spontaneously, thus in the 1st case, the substance spontaneously flow from higher chemical potential α
to lower chemical potential β, until and unless dG becomes zero to maintain an equilibrium, which is
known as escaping tendency.

Q. For the reaction

𝟐𝐍𝐚𝐇𝐒𝐎𝟒 (𝐬) ⇌ 𝐍𝐚𝟐 𝐒𝟐 𝐎𝟕 (𝐬) + 𝐇𝟐 𝐎(𝐠)
Given ∆𝐇 𝟎 = 𝟖𝟐. 𝟖𝟒 𝐤𝐉𝐦𝐨𝐥𝐞−𝟏 , ∆𝐆𝟎 = 𝟑𝟕. 𝟔 𝐤𝐉𝐦𝐨𝐥𝐞−𝟏 at 298K, Assuming ∆𝐇 𝟎 to be
constant, calculate the dissociation pressure of 𝐍𝐚𝐇𝐒𝐎𝟒 at 700K 2018

Given, ∆G0 = 37600 Jmole−1 at 298K, from Vant Hoff isotherm

∆G0 = −RT ln K P
37600 Jmole−1 = −8.314Jk −1 mole−1 × 298K × ln K P
K P,298K = 2.56 × 10−7
From Vanthoff isobar, assuming ∆H 0 remains to be fixed in the temperature range between
298K and 700K
K P,700K ∆H 0 1 1 K P,700K 82840 Jmole−1 1 1
ln = [ − ] or, ln = [ − ]
K P,298K R 298K 700K 1.56 × 10−3 8.314Jk −1 mole−1 298K 700K
K P,700K
= 4.579 × 10−9 or, K P,700K = 1.17 × 10−15 = pH2 O
2.56 × 10−7

Q. For 𝐍𝟐 𝐎𝟒 (𝐠) ⇌ 𝟐𝐍𝐎𝟐 (𝐠), by what factor would the value of 𝐊 𝐏 change if the standard state were
taken to be 0.5 bar instead of 1 bar. 2017

𝐍𝟐 𝐎𝟒 (𝐠) ⇌ 𝟐𝐍𝐎𝟐 (g)

t=0 1 0
 t=t 1 − ξeq 2ξeq
Total mole nT = (1 − ξeq ) + 2ξeq = 1 + ξeq
Mole fraction 1 − ξeq 2ξeq
( ) ( )
1 + ξeq 1 + ξeq
Partial 1 − ξeq 2ξeq
pressure ( ) P ( )P
1 + ξeq 1 + ξeq

p𝐍𝐎𝟐 2 2ξeq P 2 P P
( p ) ( ) 4ξ2eq p 4ξ2eq p
1 + ξeq p 0
KP = p 0 = = 0
= 0
𝐍𝟐 𝐎𝟒 1 − ξeq P 2
(1 − ξeq )(1 + ξeq ) (1 − ξeq )
( ) ( )
p0 1 + ξeq p0
In order to keep other term constant K P inversely varies with standard pressure p0

1 K P2 p01 1
KP ∝ or, ( )=( )= = 2 or, K P2 = 2K P1
p0 K P1 p02 0.5

Q. What would be the effect of adding 𝐂𝐚𝐂𝐎𝟑 to the following system at equilibrium at a given
temperature
𝐂𝐚𝐂𝐎𝟑 ⇌ 𝐂𝐚𝐎(𝐬) + 𝐂𝐎𝟐 (𝐠)
The equilibrium constant with respect to pressure can be written as
P
K P = ( CO2⁄P )
0

Hence the equilibrium depends on partial pressure of CO2 . It does not include CaCO3 or CaO. Hence the
incorporation of CaCO3 within the equilibrium does not shift the position of the equilibrium.

Q. Ammonium carbamate dissociates as, 𝐍𝐇𝟐 𝐂𝐎𝐎𝐍𝐇𝟒 (𝐬) ⇄ 𝟐𝐍𝐇𝟑 (𝐠) + 𝐂𝐎𝟐 (𝐠)
In a closed vessel containing ammonium carbamate in equilibrium with its vapor, ammonia is
added such that the partial pressure of 𝐍𝐇𝟑 now equals the original total pressure. Calculate the
ratio of the total pressure now to the original total pressure 2019
𝐍𝐇𝟐 𝐂𝐎𝐎𝐍𝐇𝟒 (𝐬) ⇄ 𝟐𝐍𝐇𝟑 (𝐠) + 𝐂𝐎𝟐 (𝐠)
From the stoichiometry,
p𝐍𝐇𝟑 = 2p and p𝐂𝐎𝟐 = p
pT
pT = p𝐍𝐇𝟑 + p𝐂𝐎𝟐 = 2p + p = 3p or, p =
3
p𝐍𝐇𝟑 2 p𝐂𝐎𝟐 2p 2 p p 3 4 pT 3
KP = ( ) ×( ) = ( ) × ( ) = 4( ) = ( )
p0 p0 p0 p0 p0 27 p0
Now the reaction is started with some 𝐍𝐇𝟑 (𝐠) . 𝐀𝐭 this new condition let us assume
p′𝐍𝐇𝟑 = pT (from the given condition)
As the temperature remains same K P also be same
2
p′𝐍𝐇𝟑 p′𝐂𝐎 pT 2 p′𝐂𝐎 4 pT 3
KP = ( ) ( 𝟐) = ( ) ( 𝟐) = ( )
p0 p0 p0 p0 27 p0
 4
p′𝐂𝐎𝟐 = p
27 T
Now the total pressure,
4 31 p′𝐓⁄ 31
p′𝐓 = p′𝐍𝐇𝟑 + p′𝐂𝐎𝟐 = pT + pT = p or, pT = ⁄27
27 27 T