Thermodynamics

• Thermodynamics answers the following question:

• For any reaction - defined by a set of reactants
and products set in exactly defined conditions
(temperature, pressure, concentration, etc.)  will
that reaction go forward spontaneously or not??

• It can address ANY chemical reaction, if thermo

says NO, rest assured the reaction will not
proceed, if thermo says yes, then we can progress
to the next question  how fast?
 Thermodynamics vs. Kinetics
• Kinetics Domain
 Rate of a reaction
depends on the
pathway from
reactants to products.
• Thermodynamics tells
us whether a reaction is
spontaneous based only
on the properties of
reactants and products.
 Thermodynamics
• “the branch of science that deals with
energy levels and the transfer of energy
between systems and between different
states of matter”
 Chemical Thermodynamics
• The chemistry that deals with energy
exchange, entropy, and the spontaneity of a
chemical process.
• State - Refers to the energy content of a given
system. The state is defined by specifying certain
variables such as temperature, pressure, volume
and composition.
• State Variables specifically refer to the change
inherent if a reaction proceeds because of a change
in state
• State variables are either extensive or intrinsic
• Extensive  variables which are proportional to the
quantity of matter (such as volume)
• Intrinsic  variables which are independent of
quantity, that instead describe the whole system
(such as density, temperature, and concentration)
 Systems
• System – the PART of the universe that is
under consideration. It is separated from
the rest of the universe by it’s boundaries
– Open system  when matter CAN cross the
boundary
– Closed system  when matter CANNOT cross
the boundary
– Isolated  Boundary seals matter and heat
from exchange with another system

matter
open ↔ heat closed ↔ heat isolated
 Processes
• The way a system changes states
• Adiabatic – no heat transferred
• Isothermal – constant temperature
• Isobaric – constant pressure
• Isochoric – constant volume
 Heat
• The origin of thermodynamics dealt with
heat
• Thermo considers heat, and really ANY
energy as though it were an indivisible fluid,
always flowing from higher to lower energies
• signs are + when energy flows from
surroundings to the system and – when
energy flows from system to surroundings
 Work
• Work is another kind of energy
• Different from heat
• Can flow in and out of a system and
invoke changes
• Imagine the energy required to lift a book
– that work changes the potential energy
of the book, but is not related to heat…
 1st Law of Thermodynamics
• in the Law of conservation of energy, Gibbs
in 1873 stated energy cannot be created or
destroyed, only transferred by any process

• The net change in energy is equal to the heat

that flows across a boundary minus the work
done BY the system
• U = q + w
– Where q is heat and w is work
– Some heat flowing into a system is converted to work and
therefore does not augment the internal energy
 Work and the 1st Law…
• We can think about work as a function of
pressure and volume
• dw = PdV
• Where PdV is the incremental small change
in volume at pressure associated with force
x distance (dimensions of work)
• Restate the first law as:
• dU = dq - PdV

dw
 3000 J of heat is added to a system and 2500 J of work is done by the system.
What is the change in internal energy of the system?
Known :
Heat (Q) = +3000 Joule
Work (W) = -2500 Joule
Wanted: the change in internal energy of the system
Solution :
The equation of the first law of thermodynamics
ΔU = Q-W
The sign conventions :
Q is positive if the heat added to the system
W is positive if work is done on the system
Q is negative if heat leaves the system
W is negative if work is done by the system
The change in internal energy of the system :
ΔU = 3000-2500
ΔU = 500 Joule
Internal energy increases by 500 Joule
 Energy change with volume and
heat
• Taking dU = dq – PdV from state 1 to state 2:
2 2 2

 dU   dq  P  dV
1 1 1

• Yields: U2-U1 = (q2-q1) – P(V2-V1)

• Make qp=q2-q1, multiply PV terms and rearrange:
• qp=(E2+PV2)-(E1-PV1)
• qp is MEASURABLE by measuring temperature
changes resulting from energy changes (i.e. from
a chemical reaction)
 Enthalpy (H)
• H = U + PV
• Total differential for Enthalpy is:
dH = dU + PdV + VdP
• For our integrated change in state previous:
• H1=U1-PV1 and H2=U2-PV2
H = H2-H1 = qp (AT constant P, V)
• Recall that energy is not known, only the change
is meaningful
• Therefore change is measured from a reference
state  pure elements, 25ºC, 1 bar pressure
have an enthalpy of zero  H0f
 solved problems

oxidation of sulfur dioxide to sulfur trioxide (one of most

common processes in inorganic industry) on the basis of
the standard molar enthalpies of formation of the reactants
and products (to be found in Tables in Appendix ). Decide,
whether the process is exothermic or endothermic.
SO2 (g) + O2 (g) SO3 (g)
Solution: One can find the answer in a
single step utilizing equation (1.2):
∆H = - 395.72- (-296.83) = -98.89[kJ /
mol]
The reaction is exothermic, heat is
released, the ∆H is negative
Consider this thermochemical equation.
2 CO(g) + O2(g) → 2 CO2(g) ΔH = −565 kJ
Is it exothermic or endothermic? How much energy is given off or
absorbed?
Solution
By definition, a chemical reaction that has a negative ΔH is
exothermic, meaning that this much energy—in this case, 565 kJ
—is given off by the reaction.
Test Yourself
Consider this thermochemical equation.
CO2(g) + H2(g) → CO(g) + H2O(g) ΔH = 42 kJ
Is it exothermic or endothermic? How much energy is given off or
absorbed?
Answer
Endothermic; 42 kJ are absorbed.
 Thermodynamic Processes
A PV diagram can be used to represent the state changes of a
system, provided the system is always near equilibrium.

The area under a PV curve

gives the magnitude of the
work done on a system. W>0
for compression and W<0 for
expansion.

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To go from the state (Vi, Pi) by the path (a) to the state (Vf, Pf)
requires a different amount of work then by path (b). To return to
the initial point (1) requires the work to be nonzero.

The work done on a system depends on the path taken in the PV

diagram. The work done on a system during a closed cycle can
be nonzero.
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An isothermal process
implies that both P and V
of the gas change
(PVT).

20
Thermodynamic Processes for an Ideal Gas

No work is done on a system when

its volume remains constant
(isochoric process). For an ideal
gas (provided the number of moles
remains constant), the change in
internal energy is

Q  U  nCV T .

21
For a constant pressure (isobaric) process, the change in internal
energy is

U  Q  W

where W   PV   nRT and Q  nC P T .

CP is the molar specific heat at constant

pressure. For an ideal gas CP = CV + R.

22
For a constant temperature (isothermal) process, U = 0 and the
work done on an ideal gas is

 Vi 
W  nRT ln .
 Vf 

23
Summary of Thermal Processes
The First Law of Thermodynamics

U  Q  W

W = -P(Vf - Vi)

V  V 
W = nRT ln  i  + nRT ln  i 
V  Vf
 f   

3
+ nR ( Tf - Ti )
2

24
Example (text problem ): An ideal monatomic gas is taken
through a cycle in the PV diagram.
(a) If there are 0.0200 mol of this gas, what are the temperature
and pressure at point C?

From the graph: Pc

= 98.0 kPa

Using the ideal gas law

PcVc
Tc   1180 K.
nR

25
Example continued:

(b) What is the change in internal energy of the gas as it is

taken from point A to B?

This is an isochoric process so W = 0 and U = Q.

 3  PBVB PAVA 
U  Q  nCV T  n R   
 2  nR nR 
3
  PBVB  PAVA 
2
3
 V  PB  PA   200 J
2
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Example continued:

(c) How much work is done by this gas per cycle?

The work done per cycle is the area between the curves on the
PV diagram. Here W=½VP = 66 J.

(d) What is the total change in internal energy of this gas in

one cycle?
 3  Pf Vf PiVi 
U  nCV T  n R   
 2  nR nR 
3
  Pf Vf  PiVi   0 The cycle ends where it
2 began (T = 0).
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Summary of Thermodynamic Processes

28
 The Second Law of Thermodynamics
The second law of thermodynamics (Clausius Statement): Heat
never flows spontaneously from a colder body to a hotter body.

Any process that involves dissipation of energy is not

reversible.

Any process that involves heat transfer from a hotter object

to a colder object is not reversible.

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 Entropy
Entropy is a measure of a system’s disorder.

Heat flows from objects of high temperature to objects at

low temperature because this process increases the
disorder of the system.
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 Entropy

• Like total energy, E, and enthalpy, H,

entropy is a state function.
• Therefore,
S = Sfinal  Sinitial

Chemical
Thermodynamics
 Entropy
If an amount of heat Q flows into a system at constant
temperature, then the change in entropy is

Q
S  .
T
In thermodynamics, temperature is
always represented in Kelvins

K = ºC + 273

32
Example (text problem ):
An ice cube at 0.0 C is slowly melting.
What is the change in the ice cube’s entropy for each 1.00 g of ice
that melts?

To melt one gram of ice requires 333.7 J of energy.

Q 333.7 J
The entropy change is S    1.22 J/K.
T 273 K

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• Combining the 1st and 2nd Laws of
Thermodynamics:
dU = dqrev + dw = TdS – PdV

• If a process is at constant volume, V, and

entropy, S  dU = 0  nothing happens,
energy does not change in the system
• This is EQUILIBRIUM:
– dU>0  spontaneous rxn products to reactants
– dU<0  spontaneous rxn reactants to products
 The Fundamental Equation
• Combining the first and second laws
yields:
• dU = TdS – PdV

• This is a key step, but the next one is the

cornerstone of most thermodynamic
calculations…
 o
Standard Entropy, S

• The entropy of a substance in its most stable

state at 1 atm and 25oC.
• The entropy of an ionic species in 1 M solution
at 25oC.
 Entropy and Second Law of Thermodynamics

• The second law of thermodynamics states that

all spontaneous processes are accompanied by
increase in the entropy of the universe.
– Universe = System + Surrounding;
– System: the process/reaction whose
thermodynamic change is being studied;
– Surrounding: the part of the universe that interacts
with the system.
 Conditions for Spontaneous Process

• Entropy change for a process:

Suniv = Ssys + Ssurr > 0,  process is spontaneous
Suniv = Ssys + Ssurr = 0,  process is at equilibrium

• If Ssys < 0, Ssurr > 0, and |Ssurr| > |Ssys|

• If Ssurr < 0, Ssys > 0, and |Ssys| > |Ssurr|
 Entropy Change in Chemical Reactions

• At constant temperature and pressure,

Sorxn = npSoproducts – nrSoreactants
• In general, Sorxn > 0 if np > nr

• Example-1:
• C3H8(g) + 5O2(g)  3CO2(g) + 4H2O(g), (np > nr)
Sorxn = {(3 x SoCO ) + (4 x SoH O)} – {(SoC H ) + (5 x SoO )}
2 2 3 8 2

• = {(3 x 214) + (4 x 189)}J/K – {270 + (5 x 205)}J/K

• = (642 + 756) J/K – (270 + 1025) J/K
= 103 J/K
 Entropy Change in Chemical Reactions

Sorxn < 0 if np < nr

• Example-2:
• CO(g) + 2H2(g)  CH3OH(g), (np < nr)
Sorxn = (SoCH OH) – {(SoCO) + (2 x SoH )}
3 2

• = 240 J/K – {198 J/K + (2 x 131 J/K)

• = 240 J/K – 460 J/K = -220 J/K
 Thermodynamic Free Energy
• It is the maximum amount of chemical energy
derived from a spontaneous reaction that can
be utilized to do work or to drive a
nonspontaneous process.

• It is the minimum amount of energy that must

be supplied to make a nonspontaneous
reaction occur.
 Effect of Temperature on G o

Go = Ho - TSo

• Example-1:
• For the reaction: N2(g) + 3H2(g)  2NH3(g),
Ho = -92 kJ and So = -199 J/K = -0.199 kJ/K

• At 25oC, TSo = 298 K x (-0.199 J/K) = -59.3 kJ

• Go = Ho - TSo = -92 kJ – (-59.3 kJ) = -33 kJ;
 reaction is spontaneous at 25oC

• At 250oC, TSo = 523 K x (-0.199 J/K) = -104 kJ;

• Go = Ho - TSo = -92 kJ – (-104 kJ) = 12 kJ;
 reaction is nonspontaneous at 250oC
 Effect of Temperature on G o

Go = Ho – TSo

• Example-2:
• For the reaction: CH4(g) + H2O(g)  CO(g) + 3H2(g),
Ho = 206 kJ and So = 216 J/K = 0.216 kJ/K
• At 25oC, TSo = 298 K x (0.216 J/K) = 64.4 kJ
• Go = Ho - TSo = 206 kJ – 64.4 kJ = 142 kJ;
 reaction is nonspontaneous at 25oC.

• At 1200 K, TSo = 1200 K x (0.216 J/K) = 259 kJ;

• Go = Ho - TSo = 206 kJ – 259 kJ) = -53 kJ;
 reaction is spontaneous at 1200 K
 Transition Temperature
• This is a temperature at which a reaction changes from being
spontaneous to being nonspontaneous, and vice versa, when
Qp or Qc equals 1 (standard condition)

• At transition temperature, Tr,

 Go = Ho – TrSo = 0;  Tr = Ho/So

For reaction: N2(g) + 3H2(g)  2NH3(g),

Tr = -92 kJ/(-0.199 kJ/K) = 460 K = 190oC
Under standard pressure (1 atm), this reaction is
spontaneous below 190oC, but becomes nonspontaneous
above this temperqature.
 Transition Temperature

• For reaction: CH4(g) + H2O(g)  CO(g) + 3H2(g),

 Ho = 206 kJ and So = 216 J/K = 0.216 kJ/K

 Go = Ho + TrSo = 0,

 Tr = 206 kJ/(0.216 kJ/K) = 954 K = 681oC
 Under standard pressure (1 atm), this reaction is not
spontaneous below 681oC, but becomes spontaneous above
this temperature.
 Reactions with both Ho and So < 0 favor low temperature;
 Those with both Ho and So > 0 favor high temperature.
 Free Energy and Equilibrium Constant
• For spontaneous reactions, G decreases (becomes
less negative) as the reaction proceeds towards
equilibrium;
• At equilibrium, G = 0;
• G = Go + RTlnK = 0
• Go = -RTlnK
• lnK = -Go/RT (Go calculated at temperature T)
• Equilibrium constant, K = e-(Go/RT)
Go < 0, K > 1; reaction favors products formation
Go > 0, K < 1; reaction favors reactants formation
Go = 0, K = 1; reaction favors neither reactants nor products
 Calculating K from G o

• Consider the reaction: N2(g) + 3H2(g)  2NH3(g),

• At 25oC, Go = -33 kJ

• lnK = -(-33 x 103 J/(298 K x 8.314 J/K.mol)) = 13
• K = e13 = 4.4 x 105 (reaction goes to completion)

• At 250oC, Go = 12 kJ;

• lnK = -(12 x 103 J/(523 K x 8.314 J/K.mol)) = -2.8
• K = e-2.8 = 0.061 (very little product is formed)
 Coupling Reactions

• A nonspontaneous reaction can be coupled to a

spontaneous one to make it happen.

Example:
• Fe2O3(s)  2Fe(s) + 3/2 O2(g); Go = 740 kJ (eq-1)
• CO(g) + ½ O2(g)  CO2(g); Go = -283 kJ
• 3CO(g) + 3/2 O2(g)  3CO2(g); Go = -849 kJ (eq-2)
Combining eq-1 and eq-2,
• Fe2O3(s) + 3CO(g)  2Fe(s) + 3CO2(g); Go = -109 kJ
 Coupling Reactions in Biological System

• The formation of ATP from ADP and H2PO4- is

nonspontaneous, but it can be coupled to the hydrolysis of
creatine-phosphate that has a negative Go.

• ADP + H2PO4-  ATP + H2O; Go = +30 kJ

• Creatine-phosphate  creatine + phosphate; Go = -43 kJ
Combining the two equations yields a spontaneous overall
reaction:
• Creatine-phosphate + ADP  Creatine + ATP; Go = -13 kJ
 Third Law of Thermodynamics
• The entropy of a perfect crystalline substance
is zero at absolute zero temperature (0.0 K)

• Is absolute zero temperature achievable?