Chemical thermodynamics

Thermodynamics: the study of energy and

its transformations
Thermochemistry: the sub discipline involving
chemical reactions and
energy changes
 Energy
´ Energy is defined as the capacity to do work or to
produce heat.

´ The 1st Law of Thermodynamics …. Energy is conserved

as it is converted between one form and another, it will
be neither created or destroyed, but simply change
form…thus making the energy of the universe constant!

´ Energy can be classified as either Kinetic or Potential

RECALL…….

Kinetic energy: energy associated with the motion of

atoms and molecules in a system.

KE = ½ mv2
Where m is mass (kg), v= velocity (m/s)

Temperature is a measure of the average KE of a

collection of particles in a system.
Heat vs Energy

´ Thermal energy is the energy of the object and is not

in the process of being transferred or moved.

´ Heat is kinetic energy being transferred

´ It moves from a hotter object towards cooler object until
the temperatures are the same.
´ At this point the KE’s are at equilibrium.
´ It is not a property of the substance.
 System: the part of the universe we are
studying
Surroundings: everything else

In chemistry the system is the reaction that

we are interested in and the surroundings
could be the container that the reaction
takes place in.

Usually, energy is transferred to...

Change an object’s state of motion
(1)
like fuel in a vehicle.
Cause a temperature change like
(2) a furnace warming a house.
Units of energy are
either
joules (J)
kilojoules (kJ)
James
CONVERSIONS: Prescott
Divide by 1000 to convert from J to KJ Joule
Multiply by 1000 to convert from KJ to J (1818-1889)

4184 J = 4.184 kJ
 absorbed by
In endothermic processes, heat is _________
the system.
melting
boiling
sublimation

released by
In exothermic processes, heat is ________
the system.
freezing
condensation
deposition
Water Phase Change
Diagram
• Exothermic process is any process that gives off heat –
The energy will be listed as a product.

2H2 (g) + O2 (g) 2H2O (l) + energy

H2O (g) H2O (l) + energy

Endothermic process is any process in which heat is
required by the system. The energy is listed as a reactant.

energy + 2HgO (s) 2Hg (l) + O2 (g)

energy + H2O (s) H2O (l)

 Enthalpy is used to measure the heat that is
either gained or lost by a system that is at
constant pressure.

ΔH = Hproducts – Hreactants

When ΔH is +, the system... has gained heat.(ENDO)

When ΔH is –, the system... has lost heat. (EXO)

• Enthalpy is an extensive property, meaning that…the

amount of material affects its value
Enthalpy (H)
 Thermochemical Equations

H2O (s) H2O (l) ΔH = 6.01 kJ/mol ΔH = 6.01 kJ

If you reverse a reaction, the sign of ΔH changes

H2O (l) H2O (s) ΔH =- 6.01 kJ

If you multiply both sides of the equation by a factor n,

then ΔH must change by the same factor n.

2H2O (s) 2H2O (l)

ΔH = 2 mol x 6.01 kJ/mol = 12.0 kJ

 Thermochemical Equations

The physical states of all reactants and products must be

specified in thermochemical equations.
H2O (s) H2O (l) ΔH = 6.01KJ
H2O (l) H2O (g) ΔH = 44.0 KJ

Practice Question:
How much heat is evolved when 266 g of white
phosphorus (P4) burns in air? ΔHreaction = -3013 kJ
2 H2(g) + O2(g) → 2 H2O(g) ΔH = – 483.6 kJ

What is the enthalpy change when 178 g of H2O(g)

are produced?

The space shuttle was powered

by the reaction above.
Calorimetry: the measurement of heat flow

A Calorimeter is used to measure the heat changes

molar heat (capacity): amt. of heat needed to raise

temp. of 1 mol of a substance
J/ C *mol or J/ K*mol

specific heat (capacity): amt. of heat needed to raise

temp. of 1 g of a substance
J/ C *g or J/ K*g
We calculate the heat a substance loses or gains using:

q = m c ΔT AND q = m cX

(for within a given (for between two states

state of matter) of matter when temp is
constant)
q = heat
m = amount of substance
c = substance’s heat capacity
ΔT = temperature change
cX = heat of fusion (s/l)
or heat of vaporization (l/g)
Heat capacities of metals are very low when
compared to water or other substances.
In an experiment it was determined that 59.8 J was required to
change the temperature of 25.0 g of ethylene glycol (a compound
used as antifreeze in automobile engines) by 10.0 C.

Calculate the specific heat capacity of ethylene glycol.

q = m c ΔT
 Typical Heating Curve

– q )
d (
o ve g
rem l/g
e a t
h
Temp

← l
) →
.

s/l d ( +q
a d de
s t
h ea

HEAT
 Constant Pressure Calorimetry
Calorimetry:
The measurement of heat flow
• Commonly called
“COFFEE CUP” calorimetry

• It’s used to determine any

changes in enthalpy for
reactions occurring in
solution.

• Atmospheric pressure
remains constant during the
reaction .
Practice Problem
A lead (Pb) pellet having a mass of 26.47 g at 89.98°C
was placed in a constant-pressure calorimeter
containing 100.0 mL of water. The water temperature
rose from 22.50°C to 23.17°C.

What is the specific heat of the lead pellet?

 A sketch of the initial and final situation is as follows:

We know the masses of water and the lead pellet as well as the initial and final
temperatures. Assuming no heat is lost to the surroundings, we can equate the heat lost
by the lead pellet to the heat gained by the water. Knowing the specific heat of water,
we can then calculate the specific heat of lead.
Because the heat lost by the lead pellet is equal to the heat
gained by the water,
qPb = −280.3 J.
Combustion reactions
are studied using constant
volume calorimetry.

It requires a BOMB
CALORIMETER.
We assume that no energy escapes into the
surroundings, so that the heat absorbed by the bomb
calorimeter equals the heat given off by the reaction.
 Hess’ Law 1840

´The change of enthalpy in a chemical

reaction is independent of the route by
which the chemical change occurs.

´ This is true because enthalpy is a state function , which is a value

that does not depend on the path taken
 How Hess’s Law works
● The ΔHrxns have been calculated and tabulated
for many basic reactions.

● Hess’s law allows us to put these simple

reactions together like puzzle pieces so that they
can add up to a more complicated reaction.

● By adding or subtracting the ΔHrxns, we can

determine the ΔHrxn of the more complicated
reaction.
Hess's Law is saying:

If you convert reactants A into products B, the overall

enthalpy change will be exactly the same whether you do
it in one step or two steps or however many steps.
Important things to remember when using Hess’s Law:

● If a reaction is reversed, the sign of H is also reversed.

● The size of H is directly related to the quantities of

reactants and products

● If the coefficients in a balanced reaction are multiplied

by an integer, the value of H is multiplied by the same
integer.
Calculate the enthalpy for this reaction

2C(s) + H2(g) ---> C2H2(g) ΔH° = ??? kJ

Given the following thermochemical equations:

C2H2(g) + (5/2)O2(g) ---> 2CO2(g) + H2O(ℓ) ΔH° = -1299.5 kJ

C(s) + O2(g) ---> CO2(g) ΔH° = -393.5 kJ

H2(g) + (1/2)O2(g) ---> H2O(ℓ) ΔH° = -285.8 kJ

1) Determine what must be done to the given equations to get the target equation:

a) first eq: flip it so as to put C2H2 on the product side

b) second eq: multiply it by two to get 2C
c) third eq: do nothing. We need one H2 on the reactant side and that's what we have.

2CO2(g) + H2O(ℓ) ---> C2H2(g) + (5/2)O2(g) ΔH° = +1299.5 kJ

2C(s) + 2O2(g) ---> 2CO2(g) ΔH° = -787.0 kJ
H2(g) + (1/2)O2(g) ---> H2O(ℓ) ΔH° = -285.8 kJ

Notice that the ΔH values changed as well

Add up ΔH values for our answer:
+1299.5 kJ + (-787 kJ) + (-285.8 kJ) = +226.7 kJ
Standard enthalpy of formation (ΔHf0) is the heat change
that results when one mole of a compound is formed from
its elements at STP.

Whenever a standard enthalpy change is quoted, standard

conditions are assumed.

The standard enthalpy of formation of any element in its

most stable form is zero.

ΔHf0 (O2) = 0 ΔHf0 (C, graphite) = 0

ΔH0f (O3) = 142kJ/mol ΔHf0 (C, diamond) = 1.90 kJ/mol

Some other important types of
enthalpy changes

Standard enthalpy change of combustion, ΔH°c

The standard enthalpy change of combustion of a
compound is the enthalpy change which occurs
when one mole of the compound is burned
completely in oxygen at STP .

The enthalpy change of solution (ΔH soln) is the

heat generated or absorbed when a certain amount
of solute dissolves in a certain amount of solvent at
STP.
Standard enthalpy of a reaction (ΔHorxn):
Using Hess’s law, we can easily calculate
ΔHorxn from the ΔHfo of all reactants and products by
using the following equation:

ΔHorxn = Σ (ΔH fproducts) – Σ (ΔH f reactants)

 (Look these up.
Approximate the enthalpy change for the See App. 4,
combustion of 246 g of liquid methanol. P A19.)

2 CH3OH(l) + 3 O2(g) 2 CO2(g) + 4 H2O(g)

–238.6 kJ/mol 0 kJ/mol –393.5 kJ/mol –241.8 kJ/mol
X2 X2 X4

–477.2 kJ –1754.2 kJ
ΔHorxn = (–1754.2 kJ) – (–477.2) = –1277 kJ
kJ)
So…
for 2 mol
(i.e., 64 g)
X = ΔH = –4910 kJ of CH3OH
Practice problem #1

Benzene (C6H6) burns in air to produce carbon dioxide and liquid

water. How much heat is released per mole of benzene
combusted?

The standard enthalpy of formation of benzene is 49.04 kJ/mol.

2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (g)

Practice Problem # 2
What is the Δ Hrxn for the complete
combustion of Butane, C4H10 (g)?

2 C4H10 (g) + 13 O 2(g) 8CO2 (g) + 10 H2O (g)

Chapter 17 Second Law of Thermodynamics
 Think of these commonplace
experiences:

● A Hot frying pans cool down when

taken off the stove.

● Air in a high-pressure tire shoots out

from even a small hole in its side to the
lower pressure atmosphere.

● Ice cubes melt in a warm room.

● Iron exposed to oxygen and water will

form rust.
What’s happening in each of those processes?

● Energy of some kind is changing from being localized,

concentrated, and contained to becoming more spread
out and dispersed.

● Entropy is the measurement of disorder of a system

and it is given the letter S, and it is temperature
dependent.
 43

Entropy – quantitative measure of disorder

• Entropy increases with dispersal of particles so,
entropies of gases are larger than liquids and liquid
entropies are larger than solids.

Ssolid < Sliquid < Sgas

Entropies are greater for :

- more complex molecules
- Increased temperatures (KE)
- When volume increases for gases

+ΔS ………. Entropy increases

- ΔS ………. Entropy decreases
Which substance has the greater entropy?

CO2 (s) or CO2(g)

H2 (g) at 1 atm or H2 (g) at 1.0 x 10 -2 atm

What will the overall change in entropy?

● Solid sugar is added to water to make a sugar solution.

● Water vapor condenses.
● Ice melts
 Entropy Changes in the System (ΔSsys)
When gases are produced (or consumed)
• If a reaction produces more gas molecules than it
consumes, ΔS0+
• If the total number of gas molecules diminishes, ΔS0-

What is the sign of the entropy change for the following

reaction?

2Zn (s) + O2 (g) 2ZnO (s)

The total number of gas molecules goes down….. ΔS0-

 Entropy on the Molecular Scale

• Ludwig Boltzmann described the concept of

entropy on the molecular level.

Chemical
Thermodynamics
 Entropy on the Molecular Scale

Molecules exhibit several types of motion:

Ø Translational: Movement of the entire molecule from
one place to another.
Ø Vibrational: Periodic motion of atoms within a molecule.
Ø Rotational: Rotation of the molecule on about an axis or
rotation about bonds.

Chemical
Thermodynamics
 Entropy on the Molecular Scale

• Boltzmann envisioned the motions of a sample of

molecules at a particular instant in time.
Ø This would be akin to taking a snapshot of all the
molecules.

• He referred to this sampling as a microstate of the

thermodynamic system.

Chemical
Thermodynamics
 Entropy on the Molecular Scale
Implications:

• More Particles
-> more states -> more entropy

• Higher Temp
-> more energy states -> more entropy

• Less Structure (gas vs solid)

-> more states -> more entropy
Chemical
Thermodynamics
Calculations J

The entropy change for a system(reaction) is calculated

from the entropies of the products and the reactants

ΔSosystem = Σ[So(products)] - Σ [So( reactants)]

ΔSosystem is Positive, then entropy increases

ΔSosystem is Negative,then entropy decreases

 Chemical
Thermodynamics
 Gibbs Free Energy
Gibbs Free Energy (G)
The energy associated with a chemical reaction
that can be used to do work.
What are Spontaneous Processes ?
´Spontaneous processes
are those that can proceed
without any outside
intervention.

´ For example, the gas in

vessel B will spontaneously
effuse into vessel A, but
once the gas is in both
vessels, it will not
spontaneously revert to its
original state.
Spontaneous Processes

Processes that are

spontaneous in one direction
are nonspontaneous in the
reverse direction.

Chemical
Thermodynamics
 For a constant-temperature process:
Gibbs free energy (G)

ΔG - The reaction is favorable (spontaneous) in the forward direction.

No outside energy is needed
Product formation is favored

ΔG + The reaction is unfavorable (non-spontaneous) as written.

The reaction is favorable (spontaneous) in the reverse direction
Reactant formation is favored

ΔG = 0 The reaction is at equilibrium and reactant and product

formation are equally favored
 Recap: Signs of Thermodynamic Values
Negative Positive
Enthalpy (ΔH) Exothermic Endothermic

Entropy (ΔS) Less disorder More disorder

Gibbs Free Energy Favored Not favored

(ΔG)