Comprehension-8

Chemical reactions are generally carried out at constant pressure (atmospheric pressure) so it has
been found useful to define a new state function enthalpy ( H ) .

H U PV

dH dU d ( PV )
Or at constant pressure

dH dU PdV
Hf

Uf

Vf

Hi

Ui

Vi

dH dU P dV

Or H
Combining with first law,

U PV

H q p (heat at constant pressure)

Important Points:
H is a state function & is an extensive property.
For ideal gas H f (T ) only but for real gas H f (T , P )
It has been observed that enthalpy of a given amount of substance not undergoing any
chemical/phase change depends on T&P. Hence,

H
H
dH
dT
dP
T P
P T
H
dH CP dT
dP
P T

OR
CASE-I:

CASE-II:
CASE-III:
CASE-IV:

For an ideal gas undergoing any process;

H
because there is no interaction between molecules of gas.

0
P T
dH CP dT (always)
For a real gas undergoing isobaric process; dP 0
dH CP dT
For solids & liquids dP 0 & C p Cv C
dH CdT
In chemical reaction or phase transformation in which gaseous phase is present

dH dU RT .dn

Hf

Uf

nf

Hi

Ui

ni

dH dU RT dn

OR
Or

H U ng RT

*CASE-V:

In other chemical reaction or phase transformation

r H p H f (Pr oducts) R H f (Re ac tan ts)

Enthalpy of formation of any element in its standard state assumed to

be zero

H of (element ) 0
Q.1

1 mole of a real gas change its state as

(2bar ,3l ,100 K ) (2bar ,5l , 200 K ) (3bar ,10l ,300 K )

A

If

U BC 110J & C 3R . Calculate H AC & U AC ?

H AC 4600 J ; U AC 2200 J
Ans.
m
P

Q.2

Some amount of Al ( s ) is taken with Cl2 ( g ) in a cylinder fitted with piston at

300K &1bar pressure. Now mixture is heated & Al ( s ) reacts with Cl2 ( g ) as2 Al ( s) 3Cl2 ( g ) 2 AlCl3 ( s); H 342 Kcal / mole
2
Given : area of piston is 500 cm and it moves by 48 cm . Calculate heat exchange at
constant pressure in KCal for the above process. Consider ideal gas system.
Ans. 114
Q.3

1150Kcal heat is released when following reaction is carried out at constant volume at
250 C

C7 H16 (l ) 11O2 ( g ) 7CO2 ( g ) 8H 2O(l )

Find the heat change at constant pressure.?

Q.4

1 mole of a real gas is subjected to a process from (2bar , 40l ,300 K ) (4bar ,30l , 400 K )
If change in internal energy is

Q.5

Ans. 1152.4Kcal

20KJ

then calculate enthalpy change for the process.

Ans.

24KJ

At 300 K, the standard enthalpies of formation of C6H5COOH(s), CO2 (g) & H2O(l) are
408, 393 & 286 kJ mol 1 respectively .
Calculate the heat of combustion of benzoic acid at:
(i) constant pressure
(ii) constant volume.

Ans. (i) 3201 kJ/mol (ii) 3199.75 kJ/mol

Q.6

For which of the following change U?

(A) H2 (g) + I2 (g) 2HI (g)
(B) HCl (aq)+ NaOH(aq) NaCl(aq) + H2O(l)
(C) C(s) + O2(g) CO2(g)

Q.7

(D*) N2 (g)+ 3H2(g) 2NH3(g)

Calculate net enthalpy change when one mole real gas undergo a change in state by
following path
adiabatic irrev. process
( P1,V1, T1 )
( P2 ,V1, T2 )
( P3 ,V2 , T3 )

Molar heat capacity of gas at constant volume is CV .

Ans. CV (T2 T1 ) ( PV
3 1 PV
1 1)