ENTHALPHY

LESSON VI
*
Enthalpy

Define H = U + PV
 
  state function intensive variables
locating the state

Enthalpy is also a state function

H = U + PV + VP
At constant pressure
H = U+PV
= U - W
=Q
H = QP constant pressure heating
H is expressed as a functional of T and P

for ideal gases

(proved later)
Thermochemistry
 
Heat transferred at constant volume qV = U

Heat transferred at constant pessure qP = H

Exothermic H = -ve

Endothermic H = +ve
Standard states, standard conditions
 
do not measure energies and enthalpies
absolutely but only the differences, U or H

The choice of standard state is purely a

matter of convenience

Analogy – differences in altitudes between

100 points and their elevation with respect
to sea level
*
What is the standard state ?

The standard states of a substance at a specified

temperature is its pure form at 1 bar
25oC, 1 bar:
the most stable forms of elements assign
“zero enthalpy”
o
H 298
= 0 used for chemical reactions
Standard enthalpy of formation

Standard enthalpy change for the formation

of the compound from its elements in their
reference states.
Reference state of an element is its most stable
state at the specified temperature & 1 bar

C (s) + 2H2 (g)  CH4 (g) Hf = -75 kJ

o

289K, 1 atm

From the definition, Hfo for elements  0

Hess’s Law
The standard enthalpy of an overall reaction is the sum of the
standard enthalpies of the individual reactions into which a
reaction may be divided.

Standard reaction enthalpy is the change in enthalpy when the

reactants in their standard states change to products in their
standard states.
 Hess’ Law

H1

H1 = H2 + H3 + H4 state function

Hess’s law is a simple application of the first law of thermodynamics

e.g. C (s) + 2H2 (g)  CH4 (g) H1o = ?
298K, 1 atm

C (s,graphite) + O2 (g)  CO2 (g)

Ho = -393.7 kJ
H2 (g) + ½O2(g)  H2O (l)
Ho = -285.8 kJ
CH4 (g) + 2O2 (g)  CO2 (g) + 2H2O (l)
Ho = -890.4 kJ
H1o = -393.7 + 2(-285.8) - (-890.4)
= -75 kJ/mole
Heat of Reaction (Enthalpy of Reaction)
 
Enthalpy change in a reaction, which may be
obtained from Hfo of products and reactants
Reactants  Products

I stoichiometric coefficient, + ve products,

- ve reactants
E.g. CH4 (g) + Cl2 (g)  CH3Cl (g) + HCl (g)
 Hfo/ kJ
CH3Cl -83.7
HCl -92.0
Cl2 0
CH4 -75.3
Hro = (-83.7-92.0) - (-75.3+0) = -100.4 kJ
Reactants Products

elements elements
2A + B  3C + D

0 = 3C + D - 2A - B

Generally,
0 = J J J

J denotes substances,
J are the stoichiometric numbers

*
Bond energy (enthalpy)
Assumption – the strength of the bond is
independent of the molecular environment
in which the atom pair may occur.
o
C (s,graphite) + 2H2 (g)  CH4(g)H = -75.4 kJ
H2 (g)  2H (g) H = 435.3 kJ
o

C (s,graphite)  C (g) Ho= 715.8 kJ

 C (s,graphite) + 2H2 (g)  C (g) + 4H (g)
Ho = 2(435.3)+715.8 = 1586.5 kJ
C (g) + 4H (g)  CH4 (g) H = -75.4-1586.5
= -1661.9 kJ
CH Bond enthalpy = 1661.9/4 kJ = 415.5 kJ
Temperature dependence of Hr

P
HrT
CP,P
R
Hro CP,R

298 T
What is the enthalpy change for vaporization
(enthalpy of vaporization) of water at 0oC?

H2O (l)  H2O (g)

Ho = -241.93 - (-286.1) = 44.01 kJmol-1
H2 = Ho + CP(T2-T1) assume CP,i
constant wrt T

H (273) = H (298) + CP(H2O,g) - CP (H2O,l)(273-298)

o

= 44.10 - (33.59-75.33)(-25)
= 43.0 kJ/mole
For ideal Gases:
 0 = R/P for ideal gas

0 for ideal gas

Prove PV = constant
for adiabatic reversible expansion of an ideal
gas

0 for ideal gas

Adiabatic expansion
 Reversible vs Irreversible
Non-spontaneous changes vs Spontaneous
changes
Reversibility vs Spontaneity

First law does not predict direction of changes,

cannot tell which process is spontaneous.
Only U = Q + W
THANK YOU