Thermochemistry

Study of relationships
between chemical reactions
and energy changes that
involve heat
Energy
 The ability to do work or transfer heat.
 Work: Energy used to cause an object that
has mass to move.
 Heat: Energy used to cause the
temperature of an object to rise.
Potential Energy

Energy of position
Kinetic Energy

Energy an object possesses by virtue of its

motion.
1
KE =  mv2
2
Units of Energy
 The SI unit of energy is the joule (J).
kg m2
1 J = 1 
s2
 An older, non-SI unit is still in widespread
use: The calorie (cal).
1 cal = 4.184 J
 Calorie (unit used in nutrition)
1 Cal = 1000 cal or 1 kcal
Calorie
Food Calories
704 kcal = 2945 kJ
System and Surroundings
 System – part of the universe under study
 Open system – mass and energy transfer
occurs
 Closed system – only energy transfer occurs
 Isolated system – no transfer occurs
 Surroundings – everything else outside the
system
Kinds of Systems
Basic Fact of Nature
 Systems tend to attain as low an energy
as possible.
 Transfer of Energy

a) The potential energy of this ball of

clay is increased when it is moved
from the ground to the top of the wall.
b) As the ball falls, its potential energy is
converted to kinetic energy.
c) When it hits the ground, its kinetic
energy falls to zero (since it is no
longer moving); some of the energy
does work on the ball, the rest is
dissipated as heat.
Work

 Energy used to
move an object over
some distance.
 w = F  d,
where w is work, F
is the force, and d is
the distance over
which the force is
exerted.
Heat
 Transfer of energy as a result of a
temperature difference
 From hotter object to colder one
 First Law of Thermodynamics
 Energy is neither created nor destroyed.
 In other words, the total energy of the universe is
a constant; if the system loses energy, it must be
gained by the surroundings, and vice versa.

Use Fig. 5.5

Internal Energy
The internal energy of a system is the sum of all
kinetic and potential energies of all components
of the system; we call it E.
 Absolute
value cannot be measured
 Can measure changes

Use Fig. 5.5

Internal Energy
By definition, the change in internal energy, E,
is the final energy of the system minus the initial
energy of the system:
E = Efinal − Einitial

Use Fig. 5.5

Changes in Internal Energy

 If E > 0, Efinal > Einitial

 Therefore, the system
absorbed energy from
the surroundings.
 This energy change is
called endergonic.
Changes in Internal Energy

 If E < 0, Efinal < Einitial

 Therefore, the system
released energy to the
surroundings.
 This energy change is
called exergonic.
Changes in Internal Energy

 When energy is
exchanged between
the system and the
surroundings, it is
exchanged as either
heat (q) or work (w).
 That is, E = q + w.
E, q, w, and Their Signs
Example
Calculate the change in the internal energy
for a process in which a system absorbs
140 J of heat from the surroundings and
does 85 J of work on the surroundings.
Exchange of Heat between
System and Surroundings
 When heat is absorbed by the system from
the surroundings, the process is endothermic.
Exchange of Heat between
System and Surroundings
 When heat is absorbed by the system from
the surroundings, the process is endothermic.
 When heat is released by the system to the
surroundings, the process is exothermic.
State Functions
Usually we have no way of knowing the
internal energy of a system; finding that value
is simply too complex a problem.
State Functions
 However, we do know that the internal energy
of a system is independent of the path by
which the system achieved that state.
 Inthe system below, the water could have reached
room temperature from either direction.
 State Functions
 Therefore, internal energy is a state function.
 It depends only on the present state of the
system, not on the path by which the system
arrived at that state.
 And so, E depends only on Einitial and Efinal.
State Functions

 However, q and w are

not state functions.
 Whether the battery is
shorted out or is
discharged by running
the fan, its E is the
same.
 But q and w are different
in the two cases.
State Functions: An Analogy

 Distance travelled is
not a state function
 Depends on route
taken
 A or altitude is a
state function
 Does not change
whatever path is
taken
State Functions
 https://www.youtube.com/watch?v=lL2CXp
Vti34
P-V Work

When a process
occurs in an open
container, commonly
the only work done is a
change in volume of a
gas pushing on the
surroundings (or being
pushed on by the
surroundings).
P-V Work
We can measure the work done by the gas if
the reaction is done in a vessel that has been
fitted with a piston.
w = −PV
Enthalpy
 If a process takes place at constant
pressure (as the majority of processes we
study do) and the only work done is this
pressure-volume work, we can account
for heat flow during the process by
measuring the enthalpy of the system.
 Enthalpy is the internal energy plus the
product of pressure and volume:
H = E + PV
Enthalpy
 When the system changes at constant
pressure, the change in enthalpy, H, is
H = (E + PV)
 This can be written

H = E + PV
Enthalpy
 Since E = q + w and w = −PV, we
can substitute these into the enthalpy
expression:
H = E + PV
H = (q+w) − w
H = qP
 So, at constant pressure the change in
enthalpy is the heat gained or lost.
Endothermicity and
Exothermicity
 A process is
endothermic, then,
when H is
positive.
Endothermicity and
Exothermicity
 A process is
endothermic when
H is positive.
 A process is
exothermic when
H is negative.
 Enthalpies of Reaction

The change in
enthalpy, H, is the
enthalpy of the
products minus the
enthalpy of the
reactants:

H = Hproducts − Hreactants
Enthalpies of Reaction

This quantity, Hrxn, is called the enthalpy of

reaction, or the heat of reaction.
Thermochemical Equations
 Balanced chemical equations that show
the associated enthalpy change
 When we give a numerical value for Hrxn, we
must specify the reaction involved.

2H2(g) + O2(g)  2H2O(g) H = - 483.6 kJ

The Truth about Enthalpy
1. Enthalpy is an extensive property.
2. H for a reaction in the forward direction
is equal in size, but opposite in sign, to
H for the reverse reaction.
3. H for a reaction depends on the state of
the products and the state of the
reactants.
The Truth about Enthalpy
1. Enthalpy is an extensive property.

CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) H = -890kJ

2CH4(g) + 4O2(g)  2CO2(g) + 4H2O(l) H = 2(-890kJ)

= - 1780 kJ
The Truth about Enthalpy
2. H for a reaction in the forward direction
is equal in size, but opposite in sign, to
H for the reverse reaction.

CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) H = -890kJ

CO2(g) + 2H2O(l)  CH4(g) + 2O2(g) H = +890kJ

The Truth about Enthalpy
3. H for a reaction depends on the state of
the products and the state of the
reactants.

CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) H = -890kJ

CH4(g) + 2O2(g)  CO2(g) + 2H2O(g) H = -802kJ

Example
The complete combustion of ethanol,
C2H5OH (FW = 46.0 g/mol), proceeds as
follows:
C2H5OH(l)+3O2(g)  2CO2(g)+ 3H2O(l) H = -555 kJ
What is the enthalpy change for combustion
of 15.0 g of ethanol?
Example
Hydrogen peroxide can decompose to water
and oxygen by the reaction
2H2O2(l)  2H2O(l) + O2(g) H = -196 kJ
Calculate the quantity of heat released when
5.00 g of H2O2(l) decomposes at constant
pressure.
Calorimetry Since we cannot
know the exact
enthalpy of the
reactants and
products, we
measure H through
calorimetry, the
measurement of
heat flow.

Heat lost = heat gained

qcal = - qrxn
Heat Capacity and Specific Heat

 The amount of energy required to raise the

temperature of a substance by 1 K (1C) is its
heat capacity, C.
 molar heat capacity, Cm
 Heat capacity of one mole of substance
 We define specific heat capacity (or simply
specific heat), c, as the amount of energy
required to raise the temperature of 1 g of a
substance by 1 K.
Heat Capacity and Specific Heat

Specific heat, then, is

heat transferred
Specific heat =
mass  temperature change
q
c=
m  T
Enables large bodies of water to moderate
atmospheric temperatures
Example
Large beds of rocks are used in some solar-
heated homes to store heat. Assume that
the specific heat of the rocks is 0.82 J/g-K.
(a) Calculate the quantity of heat absorbed
by 50.0 kg of rocks if their temperature
increases by 12.0 °C. (b) What
temperature change would these rocks
undergo if they emitted 450 kJ of heat?
Constant Pressure Calorimetry
By carrying out a
reaction in aqueous
solution in a simple
calorimeter such as this
one, one can indirectly
measure the heat
change for the system
by measuring the heat
change for the water in
the calorimeter.
Constant Pressure Calorimetry

Because the specific

heat for water is well
known (4.184 J/mol-K),
we can measure H for
the reaction with this
equation:
qP = m  c  T
Example
When 50.0 mL of 0.100 M AgNO3 and 50.0 mL of
0.100 M HCl are mixed in a constant pressure
calorimeter, the temperature of the mixture
increases from 22.3o to 23.11 °C. The
temperature increase is caused by the following
reaction:
AgNO3(aq) + HCl(aq)  AgCl(s) + HNO3(aq)
Calculate H for this reaction in kJ/mol AgNO3,
assuming that the combined solution has a mass
of 100.0 g and a specific heat of 4.18 J/g-°C.
Bomb Calorimetry

Reactions can be
carried out in a
sealed “bomb,” such
as this one, and
measure the heat
absorbed by the
water.
 Bomb Calorimetry

 Because the volume

in the bomb
calorimeter is
constant, what is
measured is really the
change in internal
energy, E, not H.
q
V = E
 For most reactions,
the difference is very
small.
Example
The combustion of exactly 1.000 g of
benzoic acid in a bomb calorimeter
releases 26.38 kJ of heat. If the
combustion of 0.550 g of benzoic acid
causes the temperature of the calorimeter
to increase from 22.01 to 24.27 °C,
calculate the heat capacity of the
calorimeter.
Example
A 0.5865-g sample of lactic acid (C3H6O3) is
burned in a calorimeter whose heat
capacity is 4.812 kJ/°C. The temperature
increases from 23.10 to 24.95 °C.
Calculate the heat of combustion of lactic
acid (a) per gram and (b) per mole.
Hess’s Law
 H is well known for many reactions,
and it is inconvenient to measure H
for every reaction in which we are
interested.
 However, we can estimate H using
H values that are published and the
properties of enthalpy.
Hess’s Law

Hess’s law states that

“If a reaction is carried
out in a series of
steps, H for the
overall reaction will be
equal to the sum of
the enthalpy changes
for the individual
steps.”
Hess’s Law

Because H is a state
function, the total
enthalpy change
depends only on the
initial state of the
reactants and the final
state of the products.
Hess’s Law
 https://www.youtube.com/watch?v=c8Adft
3M8mg
EXAMPLE
CH4(g) + 2 O2(g)  CO2(g) + 2 H2O(l)
CH4(g) + 2 O2(g)  CO2(g) + 2H2O(g) DH1
2H2O(g)  2 H2O(l) DH2
----------------------------------------------- -------------
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) DH = DH1 + DH2
Example
Calculate H for 2NO(g) + O2(g)  N2O4(g),
using the following information:
N2O4(g)  2NO2(g) H = +57.9 kJ
2NO(g) + O2(g)  2NO2(g) H = -113.1 kJ
Example
Carbon occurs in two forms, graphite and
diamond. The enthalpy of the combustion of
graphite is -393.5 kJ/mol, and that of diamond is
-395.4 kJ/mol:
C(graphite) + O2(g)  CO2(g) H = -393.5 kJ
C(diamond) + O2(g)  CO2(g) H = -395.4 kJ
Calculate ∆H for the conversion of graphite to
diamond: C(graphite)  C(diamond) H = ?
Example
Calculate H for the reaction:
NO(g) + O(g) NO2(g)
given the following information:
NO(g) + O3(g)  NO2(g) + O2(g) H = -198.9 kJ
O3(g)  3/2O2(g) H = -142.3 kJ
O2(g)  2O(g) H = 495.0 kJ
Enthalpies of Formation
An enthalpy of formation, Hf, is defined
as the enthalpy change for the reaction in
which a compound is made from its
constituent elements in their elemental
forms.
Standard Enthalpies of Formation
Standard enthalpies of formation, Hf, are
measured under standard conditions (25°C
and 1.00 atm pressure).
Standard Enthalpies of Formation

The standard enthalpy of formation of the

most stable form of any element is zero
because there is no formation reaction
needed when the element is already in its
standard state.
 Example
C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (l)

C3H8(g)  3C(s) + 4H2(g) H1 = -Hf°[C3H8(g)]

3C(s) + 3O2(g)  3CO2(g) H2 = 3Hf°[CO2(g)]
4H2(g) + 2O2(g)  4H2O(l) H3 = 4Hf°[H2O(l)]
--------------------------------------------- ---------------------------
C3H8(g) + 5O2(g)  3CO2(g)+ 4H2O(l) H°rxn =H1 + H2 + H3

H°rxn = H2 + H3 - H1 products reactant

Calculation of H
We can also use Hess’s law in this way:

H  = nHf(products)
 
- mHf(reactants)

where n and m are the stoichiometric

coefficients.
 Calculation of H
C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (l)
H= [3(-393.5 kJ) + 4(-285.8 kJ)] - [1(-103.85 kJ) + 5(0 kJ)]
= [(-1180.5 kJ) + (-1143.2 kJ)] - [(-103.85 kJ) + (0 kJ)]
= (-2323.7 kJ) - (-103.85 kJ)
= -2219.9 kJ
Example
Calculate the enthalpy change for the
reaction:
2H2O2(l)  2H2O(l) + O2(g)
using enthalpies of formation:
Hf°(H2O2) = -187.8 kJ/mol
Hf°(H2O) = -285.8 kJ/mol
Example
Use Table 5.3 to calculate the enthalpy change for
the combustion of 1 mol of ethanol:
C2H5OH(l) + 3O2(g)  2CO2(g) + 3H2O(l)
Example
Given the following standard enthalpy change, use
the standard enthalpies of formation to calculate
the standard enthalpy of formation of CuO(s):
CuO(s) + H2(g)  Cu(s) + H2O(l) H° = -129.7 kJ
Bond Enthalpy
 The enthalpy change, H, for the breaking
of a particular bond in one mole of a
gaseous substance.

D(Cl-Cl)
 Easy to determine for diatomic molecules
 Energy required to break molecule into atoms
Average Bond Enthalpy
 However, many important bonds, such as
the C¬H bond, exist only in polyatomic
molecules.

 D(C-H) = 16604 kJ/mole = 415 kJ/mole

Back 1
Back 2
Bond Enthalpy
 The bond enthalpy is always a positive
quantity;
 Energy is always required to break chemical
bonds.
 Conversely, energy is always released
when a bond forms between two gaseous
atoms or molecular fragments
 The greater the bond enthalpy, the
stronger the bond
Bond Enthalpy and Enthalpy of
Reactions
 Applying Hess’s Law, we can use average bond
enthalpies to determine enthalpies of reaction
1. We supply enough energy to break those bonds in
the reactants that are not present in the products.
 The enthalpy of the system is increased by the sum of the
bond enthalpies of the bonds that are broken.
2. We form the bonds in the products that were not
present in the reactants.
 This step releases energy and therefore lowers the
enthalpy of the system by the sum of the bond enthalpies
of the bonds that are formed.
Estimation of DH from Bond
Enthalpies
DH = SB.E.(bonds broken)- SB.E.(bonds formed)
Example
Using Table 8.4, estimate H for the “water
splitting reaction”:
H2O(g)  H2(g) + 1/2O2(g)
Example
Using Table 8.4, estimate H for the
reaction:
H H

N N
(g) N N (g)
+ 2 H H (g)

H H
Lattice Energy
 Energy required to completely separate
one mole of a solid ionic compound into its
gaseous ions
 MX(s)  Mm+(g) + Xn-(g) LE
 A measure of how much stabilization results
from arranging oppositely charged ions in an
ionic solid
 Na+(g) + Cl-(g)

IE EA

Na(g) Cl(g)

DHsub ½ BDE Lattice Energy (LE)

DHf

Na(s) + 1/2Cl2(g) NaCl(s)

Born-Haber Cycle
Na(s)  Na(g) Hosub = 108 kJ
Na(g)  Na+(g) + e- IE= 496 kJ
½ Cl2(g)  Cl(g) ½ D(Cl-Cl)=121 kJ

Cl(g) + e-  Cl-(g) EA = -349 kJ

Na+(g) + Cl-(g)  NaCl(s) -LE = ?
Na(s) + ½ Cl2(g)  NaCl(s) Hof,NaCl = -411 kJ
-LE = Hf,NaCl – (Hsub + IE + ½ D(Cl-Cl) + EA)
LE = 787 kJ
Example
Calculate the lattice enthalpy of calcium
oxide from the following data:
ΔH°subof Ca(s): 178 kJ/mol
IE1of Ca(g): 590 kJ/mol
IE2of Ca(g): 1150 kJ/mol
D(O=O): 495 kJ/mol
EA1 of O(g): -141 kJ/mol
EA2 of O(g): 844 kJ/mol
Δ Hf°of CaO(s): -635 kJ/mol
Spontaneous Process
 Occurs without outside intervention
 Processes that are spontaneous in one
direction are not spontaneous in the
reverse direction
Spontaneous Reactions
In general, spontaneous reactions are exothermic.
Fe2O3(s) + 2Al(s)  2 Fe(s) + Al2O3(s) ∆H = - 848 kJ
Spontaneous Reactions
But many spontaneous reactions or processes are
endothermic or even have ∆H = 0.

NH4NO3(s)  NH4NO3(aq)
Entropy, S
 One property common to spontaneous
processes is that the final state is more
disordered or random than the original.
 Spontaneity is related to an increase in
randomness.
 The thermodynamic property related to
randomness is entropy, S.
Entropy, S
 The more disordered a system, the larger its
entropy.
 Entropy is also a state function
 If S > 0 (+) = increase in randomness
 If S < 0 (-) = decrease in randomness
 Spontaneous processes in isolated systems
always have an increase in entropy. (RARE!)
 Usually concerned with open systems
Second Law of Thermodynamics

 “In any spontaneous process, there is

always an increase in the entropy of the
universe.”
Suniverse = Ssystem + Ssurroundings > 0

 No process that produces order in a

system can proceed without producing an
even larger disorder in its surroundings.
Entropy
 Can also be associated with molecular
motions within a substance
 Translationalmotion
 Vibrational motion
 Rotational motion
 As temperature of a system increases, the
amounts of energy stored in these forms
of motion increase
Third Law of Thermodynamics
 Imagine a pure substance that forms a
perfect crystalline lattice at the lowest
temperature possible
 “The entropy of a pure crystalline
substance at absolute zero is zero.”
 S (0 K) = 0
How to qualitatively predict
changes in entropy
 Positive S:
Negative S:
 Dissolution
Gas expands of its
a gas
volume
in solution
 Decrease
Dissolutioninofnumber
liquid/solid
of gaseous
solute inparticles
solutionas a
 result of a reaction
Temperature of system increases
Example
Predict whether S is positive or negative
for each process, assuming each occurs
at constant temperature:
(a) H2O(l)  H2O(g) +
(b) Ag+(aq) + Cl-(aq)  AgCl(s) -
(c) 4 Fe(s) + 3O2(g)  2Fe2O3(s) -
-
(d) N2(g) + O2(g)  2NO(g)
Absolute Entropy, S
 No comparable method exists for measuring S
for a reaction.
 However, because the third law establishes a
zero point for entropy, we can use experimental
measurements to determine the absolute value
of the entropy, S
 Careful measurement of how heat capacity changes
with T
 Usually tabulated as molar quantities, in units of
J/mol-K
Standard Entropies, So
 Entropy values of substances in their
standard states
 Puresubstance at 1 atm pressure and
temperature of reference
 Usually at 298 K
Standard Entropies, So
1. Unlike enthalpies of formation, standard molar
entropies of elements at the reference temperature of
298 K are not zero.
2. The standard molar entropies of gases are greater than
those of liquids and solids.
3. Standard molar entropies generally increase with
increasing molar mass.
4. Standard molar entropies generally increase with an
increasing number of atoms in the formula of a
substance.
∆So
So = nSo(products) - mSo(reactants)
Example
Using the given standard molar entropies,
calculate the standard entropy change,
S°, for the following reaction at 298 K:
Al2O3(s) + 3H2(g)  2Al(s) + 3H2O(g)
Substance So (J/mol-K)
Al2O3(s) 51.00
H2(g) 130.58
Al(s) 28.32
H2O(g) 188.7
Gibbs Free Energy
 Determines whether or not a process will
be spontaneous
G = H - TS
 If G < 0 the process is spontaneous as
written
 If G > 0 the process is nonspontaneous as
written
 If G = 0 the system is at equilibrium
Example
Calculate G° for a reaction for which H° =
24.6 kJ and S° = 132 J/K at 298 K. Is the
reaction spontaneous under these
conditions?
H S G Reaction characteristics
 + Always () Spontaneous at all T
+  Always (+) Nonspontaneous at all T
  () at low T Spontaneous at low T
(+) at high T Nonspontaneous at high T
+ + (+) at low T Nonspontaneous at low T
() at high T Spontaneous at high T
Standard Free Energy Changes
 Free energy is a state function
 Possible to tabulate standard free energies of
formation for substances, Gof
 Free energy of elements in standard state are
arbitrarily set to zero

Go = nGof (products) - mGof (reactants)

Example
Use data from below to calculate G° at 298
K for the combustion of methane:
CH4(g) + 2O2(g)  CO2(g) + 2H2O(g)

Substance Gof (kJ/mol)

CH4(g) -50.8
CO2(g) -394.4
H2O(g) -228.61
Next: 2nd Long Exam

THE END