UDEC 1132 – Physical Chemistry I

ENTHALPY
AND
HEAT CAPACITY
Enthalpy Changes
 So far we have discussed the INTERNAL ENERGY of a
system. A less familiar property of a system is its
ENTHALPY (H), which is defined as the internal energy
plus the product of pressure and volume:
H = U + PV

 The change in enthalpy is

∆H = ∆U + ∆(PV)
= ∆U + P∆V + V∆P ………..(1)
 We know that ∆U = q – P∆V, …………………………..(2)
Substitute (2) into (1),
∆H = (q – P∆V) + P∆V + V∆P
= q + V∆P

2
Enthalpy Changes

∆H = q + V∆P
 If we carry out a process at constant pressure,
∆P = 0, then
∆H = qp
 The subscript ‘p’ denotes that the expression
is valid only at constant pressure.

 At constant pressure, the change in enthalpy

(∆H) of the system equals the heat gained or
lost by the system.

3
 ∆U = q + w
∆U = q – P∆V

At constant VOLUME (closed container)

∆U = q – P∆V = q
∆U = qv

(A change in internal energy can be identified

with the heat supplied at constant volume)
4
Heat and Enthalpy

 Most chemical reactions encountered in the laboratory ARE

NOT at the condition of constant volume but that at constant
pressure (~ 1atm).
 The change in internal energy, U is not equal to the heat supplied
when the system is free to change its volume.
 For this, the heat liberated / absorbed is not equal to
∆U = qv
 To quantify the heat liberated / absorbed during a process of
system at constant pressure, a new thermodynamic property,
enthalpy H must be defined H = U + pV
 Hence, the enthalpy change will be
∆H = ∆U + ∆(pV) = q + w + ∆(pV).
5
 H = U + PV
∆H = q + V∆P

At constant PRESSURE (open container)

∆H = q + V∆P = q
∆H = qp

(A change in enthalpy is equal to heat supplied at constant pressure)

∆U calculated from

∆U = ∆H – ∆(PV)
= ∆H – ∆(nRT)
= ∆H – ∆ng (RT)
where
∆ng = no. of moles of product gases – no. of moles of reactant gases
6
Change of State
 Let say, a system changes from state 1 to state 2
State 1: T1, p1, V1, H1  State 2: T2, p2, V2, H2

 ∆(pV) = p2V2 – p1V1 and w = - p ∆V

 If change occurs at constant pressure in a system, p2 =
p1 = p, then ∆(pV) = pV2 – pV1 = p ∆V
 Since ∆H = ∆U + ∆(pV) = q + w + ∆(pV). Then,
∆H = q - p ∆V + p ∆V = qp
 Hence, the change in enthalpy is equal to the heat
absorbed (endothermic) or liberated (exothermic) when
a reaction occurs at the constant pressure.
7
Difference between ∆H and ∆U

 From ∆H = ∆U + ∆(pV)
 For a reaction involving liquid and solid phases, the
difference in density of the system is small.
At normal pressure of 1 atm, ∆(pV) ≈ 0
∆H ≈ ∆U (reaction involving solid and liquid)

 For a reaction involving gas phase

∆H ≠ ∆U
From the ideal gas law, pV = nRT. Then, ∆(pV) = ∆n (RT)
Hence, ∆H = ∆U + ∆n RT (at constant temperature)

8
 Class Assignment
Problem:
When 1 mol of zinc is dissolved in excess dilute hydrochloric acid in an
OPEN beaker, we find that 152.3 kJ of heat is given out (at 25°C).
Zn(s) + 2 HCl (aq) → ZnCl2 (aq) + H2(g)
What is the change in enthalpy (∆H) and what is the change in internal
energy (∆U) for this reaction?

9
 Class Assignment
Problem:

When 1 mole of ice melts at 0oC and the external pressure is

101.325 kPa, the system absorbed 6025 J heat energy. The molar
volume of ice and water are 0.0196 and 0.0180 dm3, respectively.
Calculate ∆H and ∆U.

10
 Calorimetry:
Laboratory Measurement of Heats of Reaction

Data about energy content and use is everywhere –

the calories per serving of a slice of bread, the
energy efficiency rating of a washing machine, or the
city/highway mileage of a new car.
How do we measure the heat released (or absorbed)
by a product?
The enthalpy (H) of a system in a given state cannot
be measured because we have no starting point with
which to compare it, no zero enthalpy.
However, we can measure the change in enthalpy
(ΔH) of a system.
11
Specific Heat Capacity

To measure qp, which is equal to ΔH, we construct

“surroundings” that retain the heat, and we observe
the temperature change.

Then, we relate the quantity of heat released (or

absorbed) to that temperature change through a
physical property called the specific heat capacity.

The quantity of heat (q) absorbed by an object is

proportional to its temperature change:
q
q ∞ ΔT or = constant
ΔT

12
The heat capacity is the quantity of heat required to raise the
temperature of an object by 1 K.
q
Heat capacity  [in units of J/K]
T

Specific heat capacity is the quantity of heat required to raise

the temperature of 1 g of a substance by 1 K.
q
c  [in units of J/g.K]
mass  T

Molar heat capacity is the quantity of heat required to raise

the temperature of 1 mole of a substance by 1 K.
q
C [in units of J/mol.K]
moles  T

13
SOME PHYSICS INSIGHT TO INTERNAL ENERGY

 There are three types of kinetic motions which contribute to

the heat capacity of a substance:

i) translation ii) rotation iii) vibration

 However, only translational motion will affect the temperature

change of a substance.
 Vibrational and rotational motions are not possible for
monatomic species such as the noble gas elements.
 For monatomic molecules such as He or Ar, translation is the
only kind of motion allowed.
14
 For polyatomic molecules, two additional kinds of motions
become possible.
 When a monatomic gas absorbs heat, all of the energy ends up
in translational motion, and thus goes to increase its
temperature. So these substances have the lowest heat
capacities.
 In a polyatomic gas, by contrast, the absorbed energy is
partitioned among the three kinds of motions; since only the
translational motions contribute to the temperature, the
temperature rise is smaller, and thus the heat capacity is larger.
Heat capacity of various gases

15
 Heat capacity of
dihydrogen as a
function of
temperature.

 Translational motions are active almost down to absolute zero,

so all gases possess a heat capacity of at least 3/2 R at all
temperatures.
 Rotational motions do not get started until intermediate
temperatures, typically 300-500K, so within this range heat
capacities begin to increase with temperature.
 Finally, at very high temperatures, vibrations begin to make a
significant contribution to the heat capacity. 16
Heat Capacities

 Heat capacity is defined as amount of heat required to

raise the temperature of any substance by 1 K. (SI
unit : JK-1)

dq
Heat capacity 
dT

 But because heat is not a state function, the path has

to be specified (a constant-volume or a constant
pressure path).

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Heat Capacities (Continued)

Heat capacity at constant volume, Cv

 Since U is a state function,

 U   U 
dU    dT    dV
 T V  V T

 U 
   Change in internal energy due to the T change alone.
 T V

 U 
   Change in internal energy due to the V change alone.
 V T

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 Since dU = đq – Pext dV, if only PV work is involved,

 U   U 
dq  Pext dV    dT    dV
 T V  V T

 U    U  
dq    dT  
 ext 
P   dV
 T V   V T 

 For the change at constant V, dV = 0

X (V1, T1) → X (V1, T2)

 U 
dqV    dT
 T V

19
  U 
dqV    dT
 T V

• Since the change in T and the heat transferred are readily

measured, heat capacity at constant volume, CV is defined as

dqV  U 
CV  CV   
dT hence  T V

  partial derivative

• A partial derivative is a slope calculated with all variables

except one held constant.

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 The internal energy of a
system increases as the
temperature is raised.
 This graph shows its
variation as the system is
heated at constant volume.
 The slope of the tangent to
the curve at any temperature
is the heat capacity at
constant volume at that
temperature.
 Note that, for the system
illustrated, the heat capacity
is greater at B than A.
 In this case, the internal
energy varies with the
temperature of the sample.
21
 But, we are interested only in its variation with the temperature,
the volume being held constant.

 Since the heat capacity at constant V, is readily measured, the

change in internal energy for a finite change in T at constant V:

T2
U V  
T1
CV dT  qV

 Over a small T range, Cv may be nearly constant:

UV  CV T2 T 1 

UV  CV T

22
Heat Capacities (Continued)

Heat capacity at constant pressure, Cp

 Since H is a state function,
 H   H 
dH    dT    dP
 T p  P T
 In words, the heat absorbed in a process at constant P is equal
to the change in enthalpy.

dq p  dH

 For the change at constant P, dP = 0

X (P1, T1) → X (P1, T2)
 H 
dq p    dT
 T  p

23
 Since the change in T and the heat transferred are readily measured, heat
capacity at constant pressure, Cp defined as
dq p
Cp 
dT
 H 
  
 T  p
 Since the heat capacity at constant P is readily measured, the change in
enthalpy for a finite change in T at constant P:
T2
H p  
T1
C p dT

 For gases, at a given temperature, the slope of H vs. T is steeper than that of
U vs. T
 Cp,m is larger than CV,m
 Cp,m : Molar heat capacity at constant P ; Unit J K-1 mol-1
 CV,m : Molar heat capacity at constant V ; Unit J K-1 mol-1

24
The relation between Cp and CV

 U    U  
dq    dT   pext     dV
 T V   V T 
 At constant P (P = Pext),
  U  
dq p  Cv dT   P   V   dV
  T 
 Dividing by dT and setting,
  U    V 
C p  CV  p      
  V T   T p
 For ideal gas
 U   V  nR
   0 and   
 V T  T p p
 Therefore,

C p  CV  nR or C p,m  CV ,m  R
25
 For monoatomic ideal gas,
3
- The molar translational energy, Ut = 2 RT

 U  3
CV , m     R
 T V 2

5
- The molar enthalphy, H t  RT
2

 H  5
C p ,m     R
 T p 2

 CP,m's of gases are always greater than CV,m by R owing to the

work of expansion that occurs if the gas is heated at constant
pressure.

26
 Class Assignment
Problem:
For CH4(g) at 2000 K and 1 bar, Cp,m = 94.4 J mol-1 K-1. Find Cp
of 586 g of CH4 at 2000K and 1 bar.

Solution:

27
Refresh!! HEAT CAPACITY CM

 Molar heat capacity of a material is the amount of heat required to

increase the temperature by 1oC (or 1K) of 1 mole of that material.
 Since heat is not a state function, therefore, there are two types of heat
capacity depending on the way it is measured.

Cp,m: for a change at constant pressure

Cv,m: for a change at constant volume

Both are defined as: Cp,m = dqp/dT = dH/dT dqp = Cp,m dT

Cv,m = dqv/dT = dU/dT dqv = Cv,m dT

These equations refer to heat capacity of 1 mole of substance.

28
HEAT CAPACITY CM

Difference in Cp,m and Cv,m

By using the definition H = U + pV
dH/dT = dU/dT + d(pV)/dT
Cp,m = Cv,m + d(pV)/dT
For 1 mole of gas, pV = RT
Hence, d(pV)/dT = d(RT)/dT = R
So, Cp,m = Cv,m + R
R = ideal gas constant, 8.3142 J mol-1 K-1.

29
 Summary
 We calculate ΔH of a process by measuring the heat at
constant pressure (qp).
 To do this, we determine ΔT of the surroundings and
relate it to qp through the mass of the substance and
its specific heat capacity (qp= c x mass x ΔT).
 Specific heat capacity is the quantity of energy
needed to raise the temperature of 1 g of the substance
by 1 K.
 Calorimeters measure the heat released from a system
either at constant pressure (qp= ΔH) or at constant
volume (qv= ΔU).
30
UDEC 1132 – Physical Chemistry I

REVERSIBLE
EXPANSION/
COMPRESSION
 In thermodynamic, a reversible change is a change that can be
reversed by an infinitesimal modification of a variable.
 E.g.: A gas is confined by a piston and that the external
pressure, Pext, is set equal to the pressure, P, of the confined
gas.
 For a reversible expansion,
pext  p

dw   pext dv
  p dv

 Total work of reversible expansion is

V2
w    p dv
V1

32
REVERSIBLE ISOTHERMAL COMPRESSION/ EXPANSION

 If the expansion is carried out reversibly at constant T for an ideal gas, the
external P is given by
nRT
p 
 So, V
V2
wrev    p dV
V1

V2 nRT
wrev   dV
V1 V (since the T is constant)
 V2 
wrev   nRT n  
 V1 
 
V2  V1 (expansion), n  V2   0 and w  0
 If V 
 1
 System has done work on the surroundings and internal energy ↓
 V2 
 If V2  V1 (compression), n    0 and w  0
 V1 
 Work done on the system and internal energy ↑
33
 Since for an ideal gas at constant T,
P1V1  P2V2

V2 P1

V1 P2

 wrev is also given by,

P1
wrev  nRT n
P2
P2
 nRT n
P1

34
 Class Assignment
Problem:
One mole of an ideal gas expands from 5 to 1 bar at 298K.
Calculate w for
a) A reversible expansion and
b) An expansion against a constant external pressure of 1 bar.

Solution:

35
 Class Assignment
Problem:
A piston filled with 0.0400 mole of an ideal gas expands reversibly from 50
mL to 375 mL at a constant temperature of 37oC. It absorbs 208 J of heat
during the process. Calculate q, w, ∆U, and ∆H for the process.

Solution:

36
ADIABATIC PROCESS

 In adiabatic process, no heat is gained or lost by the gas.

dq  0
dU  dq  dw

 dw (If only pV work is involved)

dU   pex dV

 Intergrate,
U2 V2

U1
dU    pex dV
V1

U  U 2  U1  w

37
 For an ideal gas, the internal energy is a function only of
temperature and so,
dU  CV dT
U2 T2

U1
dU  CV T1
dT

U  U 2  U1  CV (T2  T1 )

 Since q  0 , U  w

w  CV (T2  T1 )

 If gas expands, T2 < T1,

∆ T = -ve
 w = -ve
38
 In reversible adiabatic expansion T2 V1
CV ,m n  R n
p  pex T1 V2
 dU   p dv T 
CV ,m
 V1  R
n 2   n  
CV dT   p dV  T1   V2 

CV dT  
nRT
dV  Since C p, m  CV , m   R
V CV ,m C p ,m  CV ,m

dT dV  T2   V1 
CV   nR n   n  
T V  T1   V2 
C p ,m
 If CV is independent of T, 1
 T2   V1  CV ,m
T2dT dV
v2
    
CV    nR   T1   V2 
T1 T v1 V
 1
T V
  nR n 2 T2  V1 
CV n 2
T1 V1
  
T1  V2 
T V
CV n 2  nR n 1 C p ,m 5
T1 V2 where   
CV ,m 3 39
 By using ideal gas law,
T2 P2V2

T1 P1V1
 We can obtain,

p1 V1   p2V2
 1
T2  p2  
  
T1  p1 

 The curve P vs. V for adiabatic change is known as adiabats.

 1 
 Because γ > 1, an adiabat falls more steeply  p    than the corresponding
 V 
isotherm  p  1 
 V 
 Physical Reason:
In isothermal expansion, energy flows into the system as heat and maintains
the T, as a result, the P does not fall as much as in adiabatic expansion.
40
 An adiabat depicts the
variation of pressure with
volume when a gas
expands adiabatically.

 An adiabat for a perfect gas

undergoing reversible
expansion

 Note that the pressure

declines more steeply for
an adiabat than it does for
an isotherm because the
temperature decreases in
the former.

41
 Class Assignment

Problem:
When 1 mole of an ideal monoatomic gas is allowed to expand adiabatically
and reversibly from 22.7 L mol-1 at 1 bar and 0oC to 45.4 L mol-1, the pressure
drop to 0.315 bar.
(a) Confirm this pressure.
(b) Calculate the final temperature.
(c) How much work is done in the adiabatic expansion?

Solution:

42
 Class Assignment
When 1 mole of an ideal monoatomic gas is allowed to expand adiabatically
and reversibly from 22.7 L mol-1 at 1 bar and 0oC to volume of 45.4 Lmol-1,
the pressure drop to 0.315 bar.
(a) Confirm this pressure.
(b) Calculate the final temperature.
(c) How much work is done in the adiabatic expansion?

Solution (cont.):

43
Irreversible or reversible process?
 The shaded areas are
proportional to the amount of
work that must be done on the
gas to compress it, or that is
done on the surroundings
when the gas expands.
 The work obtained in the
surrounding in the single-step
expansion is clearly not great
enough to compress the gas
back to its initial state in
single-step compression. The
net work done is not zero. The
process is irreversible.
 The irreversible expansion/
compression can be changed
to reversible process by having
the process done in
infinitesimal steps (increase
the number of step to infinity).
44
  A reversible expansion or
compression requires:

i) A balancing of internal and

external pressures at each
infinitesimal step.

ii) Time to reestablish

equilibrium after each
infinitesimal step.

iii) An absence of friction.

 The work obtained in the surrounding in the infinite-step expansion is

exactly the amount required to compress the gas back to its initial state by
an infinite-step compression. The net work done is zero. The process is then
reversible. 45