Chemical Thermodynamics

Thermodynamics

Thermodynamics is a Greek term

which means, heat power.
Thermodynamics is the study of
energy and its transformations.
Will two (or more) substances
react when they are mixed under
specified conditions?
If they do react, what energy
changes and transfers are
associated with their reaction?
If a reaction occurs, to what
extent does it occur?

The First Law of Thermodynamics

Exothermic reactions

generate specific amounts of

heat.
This is because the potential
energies of the products are
lower than the potential
energies of the reactants.

Exothermic Equations

Processes with enthalpy changes that are negative have

heat flowing from the system and are called exothermic
processes.

H = -890 kJ

CH4(g) + 2O2 (g) CO2 (g) + 2H2O (g) + 890 kJ

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Endothermic Reactions

Endothermic reactions are those in which heat is added,

or flows, into the system, the enthalpy change of the
process has a positive value.

Ba(OH)28H2O (s) + 2NH4NO3 (s) Ba(NO3)2 (s) + 2NH3 (g) + 10H2O (l)

H = +540 kJ

The First Law of Thermodynamics

There are two basic ideas of importance for thermodynamic

systems.
1. Chemical systems tend toward a state of minimum potential
energy.
Some examples of this include:
H2O flows downhill.
Objects fall when dropped.
2. Chemical systems tend toward a state of maximum disorder.
Common examples of this are:
A mirror shatters when dropped and does not reform.
It is easy to scramble an egg and difficult to unscramble it.
Food dye when dropped into water disperses.

The First Law of Thermodynamics

This law can be stated as, The combined amount of

energy in the universe is constant.

The first law is also known as the Law of Conservation of

Energy.

Energy is neither created nor destroyed in chemical

reactions and physical changes.

Some Thermodynamic Terms

The substances involved in the

chemical and physical changes
under investigation are called the
system.
In chemistry lab, the system
is the chemicals inside the
beaker.
The environment around the
system is called the
surroundings.
The surroundings are outside
the beaker.
The system plus the
surroundings is called the
universe.

Some Thermodynamic Terms

The set of conditions that specify all of the properties of

the system is called the thermodynamic state of a

system.
For example the thermodynamic state could include:
The number of moles and identity of each substance.
The physical states of each substance.
The temperature of the system.
The pressure of the system.

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Some Thermodynamic Terms

The properties of a system that depend only on the state

of the system are called state functions.

State functions are always written using capital letters.

The value of a state function is independent of pathway.

X = X - X
final

initial

Enthalpy Change

Chemistry is commonly done in open beakers on a desk

top at atmospheric pressure.

Because atmospheric pressure only changes by small

increments, this is almost at constant pressure.
heat content
at constant pressure.

The enthalpy change, H, is the change in

Enthalpy Change

H is the heat of reaction.

This quantity will tell us if the reaction produces or
rxn

consumes heat.
If Hrxn < 0 the reaction is exothermic.
If Hrxn > 0 the reaction is endothermic.
Hrxn = Hproducts - Hreactants
Hrxn = Hsubstances produced - Hsubstances consumed

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Calorimetry

A coffee-cup calorimeter is

used to measure the amount

of heat produced (or
absorbed) in a reaction at
constant pressure
This is one method to
measure qP for reactions
in solution at constant
pressure.

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Calorimetry

If an exothermic reaction is performed in a calorimeter,

the heat evolved by the reaction is determined from the

temperature rise of the solution.
This requires a two part calculation.

Amount of heat
Amount of heat
Amount of heat

=
+
released by reaction absorbed by calorimeter absorbed by solution

Amount of heat gained by calorimeter is called the heat capacity

of the calorimeter or calorimeter constant.
The value of the calorimeter constant is determined by adding a
specific amount of heat to calorimeter and measuring the
temperature rise.

q = smT

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Calorimetry

When 3.425 kJ of heat is added to a calorimeter

containing 50.00 g of water the temperature rises from

24.00C to 36.54C. Calculate the heat capacity of the
calorimeter in J/C. The specific heat of water is 4.184 J/g
C.
Find the heat absorbed by the water in going
from 24.00C to 36.54C.

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Calorimetry

Find the heat absorbed by the calorimeter.

Take the total amount of heat added to calorimeter and
subtract the heat absorbed by the water.

(3425 J - 2623 J) = 802 J

Find the heat capacity of the calorimeter.

(heat absorbed by the calorimeter)/(temperature change)

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Calorimetry

A coffee-cup calorimeter is used to determine the heat of

reaction for the acid-base neutralization.

When we add 25.00 mL of 0.500 M NaOH at 23.000C to

25.00 mL of 0.600 M CH3COOH already in the calorimeter at
the same temperature, the resulting temperature is observed
to be 25.947C. The heat capacity of the calorimeter has
previously been determined to be 27.8 J/C. Assume that
the specific heat of the mixture is the same as that of water,
4.18 J/gC and that the density of the mixture is 1.02 g/mL.
Calculate the heat evolved.

CH3COOH(aq) + NaOH(aq) NaCH3COO(aq) + H2O(l)

Calorimetry

qrxn = 81.9 J + 628 J = 709.9 J

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Calorimetry

Determine H for the reaction under the conditions of the

experiment.
CH3COOH + NaOH NaCH3COO + H2O
We must determine the number of moles of reactants
consumed which requires a limiting reactant
calculation.

(0.0250 L NaOH)

0.500 mmol NaOH 1 mol NaCH3COO

= 0.0125 mol NaCH3COO
1 mol NaOH
1 L NaOH
0.600 mol CH3COOH 1 mol NaCH3COO
= 0.0150 mol NaCH3COO
1 L CH3COOH

1 mol CH3COOH

(25.00 mL CH COOH)
3

Finally, calculate the Hrxn based on the limiting reactant

calculation.
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Thermochemical Equations

Thermochemical equations are a balanced chemical

reaction plus the H value for the reaction.

For example, this is a thermochemical equation.

C5H12 +8O2 5CO2 + 6H2O + 3523kJ

The stoichiometric coefficients in thermochemical

equations must be interpreted as numbers of moles.

1 mol of C H

5 12 reacts with 8 mol of O2 to produce 5 mol

of CO2, 6 mol of H2O, and releasing 3523 kJ is referred to
as one mole of reactions.

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Thermochemical Equations

This is an equivalent method of writing thermochemical

equations.

H < 0 designates an exothermic reaction.

H > 0 designates an endothermic reaction
C5H12 +8O2 5CO2 + 6H2O H = - 3523kJ

Standard States and Standard Enthalpy

Changes

Thermochemical standard state conditions

The thermochemical standard T = 298.15 K.
The thermochemical standard P = 1.0000 atm.
Be careful not to confuse these values with STP.
Thermochemical standard states of matter
For pure substances in their liquid or solid phase the standard
state is the pure liquid or solid.
For gases the standard state is the gas at 1.00 atm of pressure.

For gaseous mixtures the partial pressure must be 1.00 atm.

For aqueous solutions the standard state is 1.00 M concentration.

Standard States and Standard Enthalpy

Changes

The standard molar enthalpy of formation is defined as

the enthalpy for the reaction in which one mole of a
substance is formed from its constituent elements.

The symbol for standard molar enthalpy of formation is

Hf.

The standard molar enthalpy of formation for MgCl

is:

Mg(s) + Cl2(g) MgCl2(s) + 641.8kJ/mol

H = - 641.8kJ/mol

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Standard States and Standard Enthalpy

Changes

Standard molar enthalpies of formation have been

determined for many substances and are tabulated in Table
15-1 and Appendix K in the text.
Standard molar enthalpies of elements in their most stable
forms at 298.15 K and 1.000 atm are zero.
The standard molar enthalpy of formation for phosphoric acid
is -1281 kJ/mol. Write the equation for the reaction for which
Hrxn = -1281 kJ.
P in standard state is P4(s)
Phosphoric acid in standard state is H3PO4(s)

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Standard States and Standard Enthalpy

Changes

The standard molar enthalpy of formation for phosphoric

acid is -1281 kJ/mol. Write the equation for the reaction
for which Hrxn = -1281 kJ.

P in standard state is P (s)

Phosphoric acid in standard state is H PO (s)
4

3/
2

H2(g) + 2 O2(g) + 1/4 P4(s) H3PO4(s) + 1281 kJ

Standard States and Standard Enthalpy

Changes

Calculate the enthalpy change for the reaction of one

mole of H2(g) with one mole of F2(g) to form two moles of

HF(g) at 25C and one atmosphere.

H2(g) + F2(g) 2 HF(g)

1/
2

H2(g) + 1/2 F2(g) HF(g)

H = 2 mol(271 kJ/mol) = 542 kJ

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Standard Molar Enthalpies of Formation, H

Calculate the enthalpy change for the reaction in which

15.0 g of aluminum reacts with oxygen to form Al2O3 at

25C and one atmosphere.
4 Al(s) + 3O2(g) 2Al2O3(s) H = -3352kJ/mol rxn

Example

When 50 mL of 1.0 M HCl and 50 mL of 1.0 M NaOH are

mixed in a coffee cup calorimeter, the temperature

changes from 21.0C to 27.5C. Calculate H. (density of
solution, 1.00 g/mL; specific heat, 4.18 J/gC; heat lost to
cup is negligible)
qrxn = nH
(100 mL)(1.00g/mL) = 100g

q rxn = smT = 4.18J / g C(100g )(6.5C )

q rxn = 2.7x10 3 J
H = 2.7x10 3 J / 0.050mol = 5.4x10 4 J
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Summary

Heat gained = Heat lost

q = -q
q = smT
q = CcT
q = nH
gained

lost

Enthalpy

Hydrazine, N H , is used as a rocket fuel. When 1.00g of

2

hydrazine is burned how much heat is given off?

N H +O N
H = -618 kJ
2

+ 2H2O

Hesss Law

Hesss law states that if a reaction is carried out in a

series of steps, H for the reaction will be equal to the

sum of the enthalpy changes for each step.

From the following

data calculate the
Hrxn for:
A 2C + E
Data:
A 2B
H1
B C + D
H2
E 2D
H3

A 2B
2 B 2C + 2D
2D E

H1
22
H
-H3

A 2C + E
H = H1 + 2H2 -H3

Hesss Law
Example:
CH4(g) + 2O2(g) CO(g) + 2H2O(l) + O2(g)
H = -607 kJ
CO(g) + 2H2O(l) + O2(g) CO2(g) + 2H2O(l)
H = -283 kJ
_______________________________________________________C
H4(g) + 2O2(g) CO2(g) + 2H2O(l)
H = -890 kJ
Therefore, for the reaction
CH4(g) + 2O2(g) CO2(g) + 2H2O(l), H= -890 kJ.

Note that H is sensitive to the states of the reactants and

products.

Hesss law allows us to calculate enthalpy data for reactions

that are difficult to carry out directly.

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Hesss Law
C(graphite) + O2 (g) CO2(g)
H= -393.5 kJ/mol rxn
H2 (g) + O2 (g) H2O (l)
H= -285.8 kJ/mol rxn
CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) H= -890.3 kJ/mol rxn
Determine the enthalpy of formation of CH4.
C(graphite) + 2H2 (g) CH4 (g)
C(graphite) + O2 (g) CO2(g)

1 2 (g) 2 H2O (l)

2H2 + O

H= -393.5 kJ/mol rxn

2 H= -285.8 kJ/mol rxn

CO2 (g) + 2H2O (l) CH4 (g) + 2O2 (g) H= +890.3 kJ/mol rxn

H= -393.5 + (2)(-285.8) + 890.3

H= -74.8kJ
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Hesss Law

Hesss Law in a more useful form.

For any chemical reaction at standard conditions, the
standard enthalpy change is the sum of the standard
molar enthalpies of formation of the products (each
multiplied by its coefficient in the balanced chemical
equation) minus the corresponding sum for the
reactants.

Hesss Law

Calculate the H for the following reaction from data in

Appendix K.

C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(l)

o
rxn

o
= 3H CO
+ 4H Ho 2 O)l ) H Co3 H 8 ( g ) + 5H Oo2 ( g )
2(g)

Hrxn = [3(-393.5) + 4(-285.8] - [(-103.8) + 5(0.0)]kJ

= -2219.9kJ (the reaction is exothermic.)

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Hesss Law

Application of Hesss Law and more algebra allows us to

calculate the Hf for a substance participating in a reaction
for which we know Hrxn, if we also know Hf for all other
substances in the reaction.
Given the following information, calculate Hf for H2S(g).
2 H2S(g) + 3 O2(g) 2 SO2(g) + 2 H2O(l) H = -1124kJ/mol
Hf ?
0
296.8
-285.8 kJ/mol

] [
]
{[2(296.8) + 2(285.8)] [2H + 3(0)]}kJ

Ho = 2HfoSO 2 + 2HfoH 2O 2HfoH 2S + 3HfoO 2

1124 kJ =
o
f H 2S

2H

o
f H 2S

= 41.2kJ

HfoH 2S = 20.6kJ

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Bond Energies

Bond energy is the amount of energy required to break

the bond and separate the atoms in the gas phase.

To break a bond always requires an absorption of

energy!

Hrxn = BE (reactants) - BE(products)

Bond Energies

Use the bond energies listed in Tables 15-2 and 15-3 to

estimate the heat of reaction at 25C for the reaction
below.

CH4(g) + 2O2(g) CO2(g) + 2H2O(l)

Spontaneity of Physical and Chemical Changes

Spontaneous changes happen without any continuing

outside influences.
A spontaneous change has a natural direction.
For example the rusting of iron occurs spontaneously.
Have you ever seen rust turn into iron metal without
man made interference?
The melting of ice at room temperature occurs
spontaneously.
Will water spontaneously freeze at room temperature?

Entropy, S

Entropy is a measure of the disorder or randomness of a

system.
Entropy is related to
the number of particles present.
the amount of mobility these particles have.
When:
S > 0 disorder increases (which favors spontaneity).
S < 0 disorder decreases (does not favor
spontaneity).

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Entropy

Entropy increases are expected in processes in which

liquids are formed from solids.
gases are formed.
the number of molecules of gas increases during a
chemical reaction.

the temperature of a substance increases.

2SO3(g) 2SO2(g) + O2(g)
N2(g) + 3H2(g) 2NH3(g)

ng = +1
ng = -2

S > 0
S < 0

Entropy, S

The Third Law of Thermodynamics states, The entropy

of a pure, perfect, crystalline solid at 0 K is zero.

This law permits us to measure the absolute values of the

entropy for substances.

To get the actual value of S, cool a substance to 0 K,

or as close as possible, then measure the entropy

increase as the substance heats from 0 to higher
temperatures.
Notice that Appendix K has values of S not S.

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Entropy, S

Entropy changes for reactions can be determined

similarly to H for reactions.

Entropy, S

Calculate the entropy change for the following reaction at

25C. Use appendix K.
2 NO2(g)
N2O 4(g)
S

o
rxn

o
o
= n Sproducts
n Sreactants
n

o
= SNo 2 O4(g) 2SNO
2(g)

= (304.2 J mol K ) 2(240.0 J mol K )

= 175.8 J mol K or -0.1758 kJ mol K

The negative sign of S indicates that the system is more

ordered.
If the reaction is reversed the sign of S changes.
For the reverse reaction S= +0.1758 kJ/K
The + sign indicates the system is more disordered.

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Entropy, S

Calculate S for the reaction below.

Use appendix K.

3 NO( g)
N2O( g) + NO2( g)
0
0
S0298 = SN0 2 O(g) + SNO
3 SNO
2( g)
( g)

= 219.7 + 240.0 - 3 ( 210.4 ) J mol K

= 172.4 J mol K or -0.1724

kJ

mol K

Changes in S are usually quite small compared to E

and H.
Notice that S has units of only a fraction of a kJ while
E and H values are much larger numbers of kJ.

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The Second Law of Thermodynamics

The second law of thermodynamics states, In

spontaneous changes the universe tends towards a state

of greater disorder.
Spontaneous processes have two requirements:
The free energy change of the system must be
negative.
The entropy of universe must increase.

The Two Aspects of Spontaneity

An exothermic reaction does not ensure spontaneity.

For example, the freezing of water is exothermic but
spontaneous only below 0C.

An increase in disorder of the system also does not insure

spontaneity.

It is a proper combination of exothermicity and disorder

that determines spontaneity.

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Free Energy Change, G, and Spontaneity

In the mid 1800s J. Willard Gibbs determined the

relationship of enthalpy, H, and entropy, S, that best

describes the maximum useful energy obtainable in the
form of work from a process at constant temperature and
pressure.
The relationship also describes the spontaneity of a
system.
The relationship is a new state function, G, the Gibbs
Free Energy.

G = H - TS
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Free Energy Change, G, and Spontaneity

The change in the Gibbs Free Energy, G, is a reliable

indicator of spontaneity of a physical process or chemical

reaction.
G does not tell us how quickly the process occurs.
Sign conventions for G.
G > 0 reaction is nonspontaneous
G = 0 system is at equilibrium
G < 0 reaction is spontaneous

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Free Energy Change, G, and Spontaneity

Changes in free energy obey the same type of

relationship we have described for enthalpy, H, and

entropy, S, changes.

Free Energy Change, G, and Spontaneity

Calculate G for the reaction in Example 15-8.

Use

appendix K.

C 3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O()

o
Grxn
= [3Gof CO2(g) + 4Gof H2 O( ) ] [Gof C3H(8g) + 5Gof O2(g) ]

= {[3(394.4) + 4(237.3)] [(23.49) + 5(0)]} kJ mol

= 2108.9 kJ mol

G < 0, so the reaction is spontaneous at standard state

conditions.

If the reaction is reversed:

G > 0, and the reaction is nonspontaneous at
standard state conditions.

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Free Energy

What is the normal boiling point of bromine?

Br2 (l) Br2 (g)
Hrxn = 30.91 kJ/mol
Srxn = 0.0932 kJ/mol-K
G = H - TS; At boiling, G = 0
H = TS
T = H/S = 30.91 kJ/mol/0.0932 kJ/mol-K
T = 332 K (59C)
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Gibbs Free Energy

Go = Ho - TSo
Ho

So

Go

Reaction

exo(-)

increase(+)

spontaneous

endo(+)

decrease(-)

non-spontaneous

exo(-)

decrease(-)

+/-

spontaneous if
H>TS

endo(+)

increase(+)

-/+

spontaneous if
H<TS

Free Energy and Temperature

SiO2 (s) + C(graphite) + 2Cl2 (g) SiCl4 (g) + 2CO2 (g)
G = H - TS
0 = H - TS
0=-
Therefore, if TS > H the reaction is spontaneous.

H = 32.9 kJ/mol; S = 0.2265 kJ/mol-K

T = H/S = 32.9/0.2265 = 145 K
spontaneous above 145K