Enthalpy and

Adiabatic Process

CHEH 240 Lecture 4

 Heat Capacity, C
The change in the internal energy U produced by the transfer of heat q to a system when no work
is done is given by:
∆U =q (V is constant, no work is done)
In words, “ the heat absorbed by a closed system in a process in which no work is done is equal to
the increase in the internal energy of the system.”
The amount of heat transferred is (usually) proportional to the temperature gradient and the
proportionality constant is the heat capacity.
dq = C dT

q = dq = C dT
T2
q
q  C  dT  q  C (T2  T1 )  C T and C
T1
T
Heat capacity is an easily measured property. A measured amount of energy in the form of heat is
put into a system [usually by electrical heating] and the temperature change is measured with a
thermometer or thermocouple.

2
• Constant Volume Heat Capacity (Cv)

This is an easy condition to fulfill for gases in a firm

container but a difficult condition to achieve for solids
and liquids if the temperature is changed –requires
hundreds of atms pressure to keep its volume constant
when heated.

when heat (dq)v is added to the system held at constant volume

and the temperature change is dT.
The constant volume heat capacity is

Cv = (dq)v / dT and (dq)v = Cv dT

If Cv does not change with temperature then integrating gives

(q)v = Cv ∆T True for constant volume process. 3

When V = constant dV = 0 and so the work dw = -pext dV =0 .
Thus dU = (dq)v + 0 = CV dT and

U =∫ dU = (q)v = Cv T
(constant volume process)

This means differentiate U with respect to T but treat V

as a constant. This is called a partial derivative and is
written as:

The symbol ∂ is pronounced ‘di’ and the

partial is di U over di T at constant V
4
• Constant Pressure Heat Capacity (Cp)
Changing T or V but ensuring that p stays constant. This is an easy
condition to satisfy for solids and liquids if we do the process in
the open at constant atmospheric pressure = 1 atm.
We don’t have to do anything special to satisfy the path. That’s
why a constant pressure path is even more special than a
constant volume path.
For a gas, a constant weight on the piston keeps
the pressure constant. Heating the gas will
increase the volume of the gas but the pressure
will remain the same.

5
Since ∆U = q + W
For a reversible and constant pressure process the first law
gives ∆U = qp -p ∆V
For the initial and final states:

∆H = H2 – H1 = qp
6
 Enthalpy
“The heat absorbed in a process at constant pressure is equal to
the change in enthalpy if the only work done is reversible
pressure-volume work”

∆H = H2 – H1 = qp

This means that any H for a system can be

obtained by going from the initial to final state
under constant pressure conditions and measuring
the heat that develops.

7
For example, the heat of a reaction H can be obtained by doing a
reaction in the open (a constant pressure path) and measuring the
resulting heat. This is very convenient because we can get what we
want, the heat of a reaction, without having to do anything very special
with regard to conditions i.e. establishing the path.
It’s for this reason that the constant pressure path is the most
special of all and why we have tables of H values and not U
values.

8
The relation between the two heat capacities can be
derived easily for IDEAL gases.

H = U + pV and pV = nRT
dH = dU + d(pV) and d(pV) = nRdT
dH = dU + nRdT
For an ideal gas
dH = Cp dT and dU = CV dT

Cp dT = CV dT +nR dT
Thus dividing by dT gives
Cp – CV = nR or
Cp,m – CV,m = R = 8.314 J K-1 mol-1

Since Cp,m values for gases are about 30 J K-1 mol-1

the difference is large.
9
 Cp,m – CV,m = R
Cp,m = CV,m + R

For mono atomic gas

CV,m = 3/2 R
and Cp,m = 5/2 R

10
 q = ΔU − w
Δ H = ΔU+ Δ PV
•Heat is the Energy transfer due to thermal
interactions, like, heating water.
•Enthalpy is the TOTAL energy of the thermodynamic
system, including Internal Energy and its Pressure-
Volume Energy (Work system does to displace the
environment to do its work)
•For many processes involving solutions and not
gases, it is safe to assume that ΔPV=0 and
11
What is the difference between Enthalpy and Heat?

- Heat is the form of energy transfer from a high

temperature to a lower temperature.
- Enthalpy is the heat transfer at a constant pressure.
- Enthalpy cannot be measured directly. Rather, the
heat added or lost from the system gives the
enthalpy change.
- Enthalpy is a function of the state, where heat isn’t.

12
10 g of CO2 (molecular weight 44 g mol-1, Cp,m = 46.5 J/K mol)
behaving as an ideal gas are heated from 200 K to 430 K reversibly and
isobarically at p = 0.75 atm. Analyze the signs and the equations to be
used for w, q, U and H. Calculate the values and then comment on
the reasonableness of the answers. First write as much information
about the initial and final state as possible.

Analysis
(i) isobaric, reversible w = -pV; gas expansion w<0
(ii) isobaric  qp = CpT = nCp,mT = H; T increases  heat
absorbed q>0
U = w + q ; since heat absorbed and T increases U > 0
13
Most work, heat and energy change calculations are less than 5 kJ unless
the number of moles is very large or the changes in pressure, temperature
or volume are very large
Calculations and Comments
(i) work
w = - pV = -0.75 atm x(10.67 – 4.967)L = - 3.77 L atm x 101.3 J/L atm =
-382 J sign is as predicted (magnitude < 5 kJ is reasonable)
(ii) heat
qp = nCp,mT = 0.227 mol x 46.5 J K-1 mol-1 x (430 –200) K
= 2428 J or 2.43 kJ = H sign as predicted magnitude OK
(iii) energy
U = w + q = -382 + 2428 = 2046 J or 2.05 kJ sign as predicted
magnitude OK
14
 Adiabatic process with gases
If a gas system expands adiabatically (no heat is gained or lost by the gas)
against external pressure pext

dU = dw = -pext dV
This apply for any adiabatic process, reversible or
irreversible , if PV work kind.
If pext = zero (adiabatic expand into vacuum) no work is done
and there is no change in U. If the expand is opposed by pext,
work is done on the surrounding, and the temperature drops as
internal energy converted into work, so
U2 V2


U1
U    pext dV
V1

U  U 2  U1  W
For an ideal gas, U is a function of T only so,
dU  C dt 15
 If CV is independent of temperature,

U2 T2


U1
dU  CV 
T1
dT

U  U 2  U1  CV (T2  T1 )
T2

W  U  CV 
T1
dT  CV (T2  T1 )

16
 Two moles of gas at 1 bar and 298 K are compressed at
constant T by use of 5 bar pressure. How much work is
done on gas? If the compression is driven by 100 kg mass,
how far will it fall in the earth’s gravitational filed?
What is given:
n = 2 moles
p1 = 1 bar
p2 = 5 bar
T= 298 K
Compression === work is add to the system ==== positive
 nRT nRT 
W   p 2 (V2  V1 )   p 2 
 p  

 2 p1 
 p2 
W   nRT 
 1  

 p1 

W = -(2 mole) (8.314 J K-1 mole-1)(298 K) (1-(5/1))

=+19820 J = 19.82 kJ
Work = h m g
H = work/(m g) = 19820 J /[(100kg)(9.8 m s-2)] =
20.22 m 17
10 g of CO2 (molecular weight 44 g mol-1, Cp,m = 46.5 J/K mol)
behaving as an ideal gas are heated from 200 K to 430 K reversibly and
isobarically at p = 0.75 atm. Analyze the signs and the equations to be
used for w, q, U and H. Calculate the values and then comment on
the reasonableness of the answers. First write as much information
about the initial and final state as possible.

Analysis
(i) isobaric, reversible w = -pV; gas expansion w<0
(ii) isobaric  qp = CpT = nCp,mT = H; T increases  heat
absorbed q>0
U = w + q ; since heat absorbed and T increases U > 0
18
Most work, heat and energy change calculations are less than 5 kJ unless
the number of moles is very large or the changes in pressure, temperature
or volume are very large
Calculations and Comments
(i) work
w = - pV = -0.75 atm x(10.67 – 4.967)L = - 3.77 L atm x 101.3 J/L atm =
-382 J sign is as predicted (magnitude < 5 kJ is reasonable)
(ii) heat
qp = nCp,mT = 0.227 mol x 46.5 J K-1 mol-1 x (430 –200) K
= 2428 J or 2.43 kJ = H sign as predicted magnitude OK
(iii) energy
U = w + q = -382 + 2428 = 2046 J or 2.05 kJ sign as predicted
magnitude OK
19
 For an ideal monatomic gas
ΔU=nCV ΔT
(all the energy going into heating the gas, no
work is being done because ΔV = 0) &
ΔH = ΔU + Δ(PV) or
ΔH = ΔU + nRΔT or
ΔH = nCV ΔT + nRΔT = n(CV+R) ΔT or
ΔH = nCP ΔT
 A mole of monoatomic ideal gas at 1 bar and 273.15 K is allowed to
expand adiabatically against pressure 0.395 bar until equilibrium is
reached (a) what is the final temperature, (b) what is the final volume,
(c) how much work is done, (d) what is the change in the internal energy
of the gas?

What is given:
n = 1 mole, p1 = 1 bar = 105 Pa (N/m2), T = 273.15 K, p2 = 0.395 bar =
0.395 x 105 Pa (N/m2), Cv = 3/2 R

(a) final temperature

nRT (1mol)(8.314 JK 1mol 1 )(2273.15K )
V1    0.0227 m 3

P1 1x105 Pa
W   pext (V2  V1 )  CV (T2  T1 )
3
W  0.395 x10 Pa (V2  0.0227m )  R(T2  273.15)
5 3

2
nRT2 (1mol)(8.314 JK 1mol 1 )(T2 )
V2  
P2 0.395 x105 Pa
21
T can be calculated = 207.09 K
(b) V2
nRT2 (1mol)(8.314 JK 1mol 1 )(207.04 K )
V2    0.04358m 3

P2 0.395 x105 Pa
(c) W = -pext(V2-V1) = -(0.395 x 105 Pa)(0.04358m3-
0.0227m3) = -825 J mol-1

(d) ∆U = W =-pext(V2-V1) = Cv(T2-T1) =(3/2)R x (207.04 K-

273.15 K) = -825 J mol-1

22
 For adiabatic reversible expansion process:
RT
CV ,m dT   PdVm   dVm
Vm
dT R
CV ,m   dVm
T Vm

If the heat capacity is independent of temperature T,

T 2
dT
then
V
dV
2 ,m

CV ,m   R  m

T1
T V1,m
Vm
T2 V1,m V1,m
CV ,m ln  R ln  (C p ,m  CV ,m ) ln
T1 V2,m V2,m
T2 C p ,m V1,m
ln  (  1) ln
T1 CV ,m V2,m 23
  C p ,m 
 1   1
 T2   V1,m  C
 V ,m 

 V1,m 
       
  
 T1   V2,m   V2 , m 
 C p ,m 
   

 C v , m 
 p2V2,m   T2 
From the ideal gas law:   
 pV  T 
 1 1,m   1 
 1
 p2V2,m   V1,m 
  
 V 

 p1V1, m   2, m 

 
 p2V2,m  p1V1,m

24
 One mole of an ideal mono atomic gas is allowed to expand
adiabatically and reversibly from 22.7 L mol-1 at 1 bar and 0ºC to a
volume of 45.4 L mol-1.
Calculate the final pressure and temperature.
How much work is done? Where α = [(5/2)R/(3/2)R] = 5/3
What is given:
n = 1 mole, V1,m =22.7 L mol-1 p1 = 1 bar , T1= 0ºC = 273.15 K
V2,m =45.4 L mol-1 , α = 5/3
p2 = ? bar , T2= ? K
 
p2V2,m  p1V1,m

 V1,m 
5/ 3
 22.7 L.mol  1
p2  p1    1bar 
  1
  0.315bar
V
 2, m   45.4 L.mol 
 1 5 
 V1,m  1  3 1 
 22.7 L.mol 
T2  T1  
  (273.15K ) 
1 
 172.07 K
 V2 , m   45.4 L.mol 
25
 T2
W  C
T1
V ,m dT  CV ,m T 

3
   R(172.07 K  273.15K )
2
1
 1261J .mol
Work is negative (expansion) the sign is correct

26
 Thermochemistry
“It deal with heat produced by chemical reactions and solution
processes”

q is negative q is positive

27
 STANDARD STATE
H values in tables are given for substances in a definite state, called
the standard state indicated by superscript q.
The standard state of a substance at a particular temperature is the
most stable state of the substance under 1 atm of pressure [can also
use 1 bar = 105 Pa = 0.9869 atm].
Note that the standard state can be for any temperature but for practical
purposes we use 25 °C or 298 K. The standard state of some
elements at 1 atm and 298 K is given below.

28
Standard Heat of Reaction:
The standard heat of a reaction is the sum of the standard heats of
formation of products minus the sum of the standard heats of formation of
reactants [Don’t forget the stoichiometric coefficients of the balanced
reaction].

Note that the units of the heat of formation are kJ mol-1 and that the
stoichiometric coefficient n has no units. Thus the units of the heat of
reaction are kJ mol-1. The mol-1 unit is to be understood as “per mol of
reaction as written”. This ensures that if the reaction is multiplied by any
numeric factor then the heat of reaction will increase by the same factor.
Thus for the reaction.

29
 DEFINITION of Standard Heat of Formation of Compounds:
This is the heat required to form the compound [in its most stable form] from its
constituent elements in their standard states. Thus we need to know the most
stable state of the compound and elements in order to be able to write the
formation reaction.
For example, the most stable state of water at 1 atm, 298K is the liquid state
and its heat of formation is not the same as that of gaseous water (steam).
To write the formation reaction just look at the elements that make up the
compound and write the most stable state of these elements.

30
 HESS’S LAW: The standard heat of an overall reaction is the sum of
heats of individual reactions into which an overall reaction can be broken
down i.e. you can add, subtract and multiply [do an algebra on] individual
reactions and their heats to arrive at the overall reaction and its heat.

Example:
How to get the fHq for the oxidation of glycine(aq)  urea(aq)
using known data. This reaction is of interest since urea is the
main oxidative metabolic product of amino acids.

31
 Reaction Enthalpy [Hr]
Heat production is connected with chemical reaction.
From the first law of thermodynamics:
dU = dq – pdV
dq = dU + pdV
and H = U +pV
By differential: dH = dU + pdV + Vdp
By substitution: dH = dq + Vdp
For a system containing n species and at constant p:
N
Partial molar enthalpies of species i  dH  H
i 1
i ,m dn i

ni is the amount of substance i

32
But dn i  n i d for a reaction
Where n i is the stoichiometric number of reactant i
and
 is the extent of reaction
N
dH  dq p  n
i 1
i H i , m d
The reaction enthalpy will be:
 dH   dq p  N
 r H         n i H i ,m
 d T ,p  d  i 1
It is the derivative of the enthalpy of the system with
respect to the extent of reaction.
If one mole of reaction occur===
   1mol
and ∆H =(1mol) ∆rH

33
What is the meaning of one mole of rxn?

 H 1O H O
2 2 2
one mole of rxn
2
 2H 2  O 2  2H 2 O two mole of rxn
 ∆H has SI units (Joule) whereas ∆rH has SI units Joule
mol-1
 If reactants and products are in their standard states:
N
r H   n i H i ,m
i 1

34
The standard states are define as follow:
1. A pure gas at a given temperature is ideal gas at one bar pressure.
2. A pure liquid at a given temperature and at one bar pressure.
3. A pure crystalline substance at a given temperature and at one bar
pressure.
4. A substance as solution with 1 molality (1mol kg-1) at a given
temperature and at one bar pressure.

35
Thermochemistry LAWs
 Lavoisier: The heat absorbed in decomposing a
compound must be equal to the heat evolved in
its formation under the same conditions.
 Hess: The overall heat of a chemical reactions
at constant pressure is the same, regardless of
the intermediate steps involved.
 Both principles are in good agreement with the
First Law of Thermochemistry.
 It is possible to calculate the enthalpy changes
for reactions that cannot be studied directly.

36
Calculate ∆rH for a reaction when carbon burns to CO in a limited
amount of O2 from these reactions:
(a) C + ½ O2(g) CO(g) ∆rH =??
(b) C + O2(g) CO2(g) ∆rH =-393.509 kJ mol-1
(c) CO(g) + ½ O2(g) CO2(g) ∆rH =-282.984 kJ mol-1

 By multiplying eqaution (c) x -1

(d) CO2(g) CO(g) + ½ O2(g) ∆rH =+282.984 kJ mol-1
Add (b) + (d)
(b) C + O2(g) CO2(g) ∆rH =-393.509 kJ mol-1
====================================================
(a) C + ½ O2(g) CO(g) ∆rH =(+282.984 - 393.509)
= -110.525 kJ mol-1

37
How to calculate the heat of rxn at any temperature:

 We know that at constant pressure dH = Cp dT

 We can adapt this equation to the heat of a reaction rH and
introduce a term, rCp, which is similar in form to rH. It is the
(constant pressure) heat capacity of the reaction.
For reactants and products in their standard states

38
What is the value of rH° at 0K for the reaction:
H 2( g )  2 H ( g )
where fH° at 298 = 217.999 kJ mol-1 for H gas
H0° - H298° = -8.468 kJ mol-1 for H2 gas
H0° - H298° = -6.197 kJ mol-1 for H gas

rH° (298K) = 2fH° for H gas = 2 x (217.999) = 435.998

kJ mol-1

................H 2( g ) 
0K
2H( g )
o
H 298  H 0o  ..................  ....H 0o  H 298
o

................H 2( g ) 298
 K
 2H( g )

39
Calculate the heat of the following reaction
at 398 K given
values at 298 K
 There are situations where we would like to know the heat of a
reaction at other than 298 with high accuracy.
 For example, in industrial large scale reactions heat from an
exothermic reaction must be accurately known to design the
correct cooling devices so that reactors do not overheat and cause
disasters. In these cases, heat capacity of compounds must be
known as a function of temperature.
 This will provide an equation for the heat capacity of the reaction
as a function of temperature and hence the general Kirchhoff
equation can be integrated. Heat Capacity data for a compound
have been. fitted empirically to the equation.

a, b and c are constants

(independent of temperature)
for a compound that can be
found in tables.
41
The heat capacity for the reaction can then be written

Since we have an equation for rCp as a function of temperature we

can substitute into the integral and do the integration.

Integrating gives the temperature dependent Kirchhoff equation.

42
Enthalpy of Solution
 When a solute dissolved in a solvent, heat may be absorbs or
evolves.
 Heat of solution: it is the enthalpy change for the solution of 1
mole of solute in n moles of solvent. It is depend on the final
concentration of the solution.
 When the solute is dissolved, heat always absorbed to overcome
the attraction forces between the molecules or ions of the solid
solute (Lattice energy)
 Another process is the strong attraction between the molecules or
ions (solvation or hydration in case of water) with solvent which
evolves heat.
 The energy required to separate Na+ from Cl- in crystalline solid
when is dissolved in water is about the same as hydration energy,
q, is small positive value at 25 oC.
 When Na2SO4 is dissolved in water at 25 oC, there is an evolution of
heat because the energy of hydration of ions is greater than the
energy required to separate the ions from the crystal. 43
Calculate the heat of formation of Cl- ion in water from the reaction
HCl(g) H+ (aq) + Cl-(aq) ∆rH° =-75.1 kJ

• ∆rH° = ∑ ∆rH° (product) - ∑ ∆rH° (reactants)

• = (∆fH° H+ (aq) + ∆fH° Cl-(aq) ) - ∆fH° HCl (g)
• ∆fH° H+ (aq) = 0.0 (agreement)
• ∆fH° HCl (g) = -92.3 kJ (from the tables)

• ∆rH° = -75.1 kJ = (0.0 + ∆fH° Cl-(aq) ) – (-

92.3)
• ∆fH° Cl-(aq) = -167.4 kJ

44
Enthalpy of neutralization
 The heat produced when one mole of H+ ion
(acid) react with one mole of OH- (base) in
dilute solution to form one mole of water.
 rH° for strong acid with strong base is
constant and equal -55.835 kJmol-1 . This is due
to the complete dissociation of both the strong
acid and strong base and the formation of salt.
 When a weak acid or base is neutralized, the
heat of neutralization is less, due to the heat
absorbed to dissociate the weak acid or base .

45
Calculate the ionization enthalpy (∆iH°) of HCN from the reaction:
HCN(aq) +OH- CN- (aq) + H2O(l) ∆rH° =-10.3 kJ/mol

This reaction is consisting of:

a) HCN(aq) CN- (aq) + H+(aq) ∆iH°=∆rH°
b) H+(aq) +OH -(aq) H2O(l) ∆rH° =-55.85 kJ/mol
Equation a) + equation b)

∆iH° + (-55.85) = -10.3 kJ/mol

∆iH° HCN(aq) = 45.55 kJ/mol

46