Chapter 16 - Thermochemistry

Chapter 16 - Thermochemistry
There is an energy change that occurs with each chemical

reaction. A chemical reaction is classified as either ……
Endothermic (Heat is taken in from the

surroundings. Without that extra heat, the
reaction can’t occur.) Feel Cold.
Exothermic (Heat is released to the

surroundings. You don’t need to put heat
into this type of reaction in order to make it
happen.) Feel Hot.
• Energy (E)
the capacity to do work or to produce heat.
• Heat (q)
transfer of energy that always flows from a
warmer object to a cooler object.
Measuring Heat
One calorie (cal) is the quantity of heat that
raises the temperature of 1 gram of pure water
by 1oC.
1 Calorie = 1000 cal = 1 kcal = 4186 J

1 Calorie = 1000 cal = 1 kcal = 4186 J
How many joules of energy will a 175 Calorie granola bar

release?
• Specific heat capacity (specific heat) is represented by
the letter “Cp”.
• It is the amount of heat it takes to raise the temperature

of 1 gram of a substance by 1oC.
Cp = q J
mΔT g x oC
Rearranged:
q = m Cp ΔT
Specific Heat Capacities (p. 533)
Water (l) 4.18 J/(g x oC)
Ethanol 2.44 J/(g x oC)
Aluminum 0.897 J/(g x oC)

Iron 0.449 J/(g x oC)
Silver 0.235 J/(g x oC)
Lead 0.129 J/(g x oC)
Gold 0.129 J/(g x oC)
Cp = q/mΔT
The temperature of a piece of copper with a mass of
0.0954 kg changes from 25.0 oC to 48oC when the metal
absorbs 849 J of heat.
a. Is this heat transfer endothermic or exothermic?
b. What is the specific heat of copper?

When 435 J of heat is added to 0.0034 kg of olive oil at
21oC, the temperature increases to 85oC.
a. Is this heat transfer endothermic or exothermic?
b. What is the specific heat of olive oil?

How much heat must be added to 50 g of water to
increase the temperature from 23 oC to 100 oC?
The specific heat of water is 4.18 J/(g x oC)
How much heat must be released to 30 g of iron
to decrease the temperature from 230 oC to 25 oC?
The specific heat of iron is 0.449 J/(g x oC)
Endothermic vs Exothermic (sign designation “q”)
• Endothermic Process:
Heat flows from the surroundings into the system.
T2 – T1 = positive number
heat (q) = positive number
• Exothermic Process:
Heat flows from the system to the surroundings.
T2 – T1 = negative number
heat (q) = negative number
Calorimetry
• The accurate and precise measurement of
heat change for chemical and physical
processes.
• A Calorimeter is used to measure the amount

of heat absorbed or released during chemical
or physical processes.
Exothermic
The heat lost by the system must equal the heat
gained by the surroundings.
-qsystem = +qsurroundings
Endothermic
The heat gained by the system must be equal to
the heat lost by the surroundings.
+qsystem = -qsurroundings
The temperature of hot gold changes by 312 oC when 53 g of
it is placed in a bucket of cold water. How much heat is
absorbed or released by the gold? (Cp = 0.129 J/goC )
How much heat is absorbed or released by the water?
If the final temperature of the gold is 67oC, what is the final

temperature of the water in the bucket?
Cal orimetry proble m
A sample of lead with a mass of 58.9 g is heated to a

temperature of 389.1 K and placed in a container of
water at 285.3 K. The final temperature of the lead
and water is 290.1 K. What mass of water was in the
container? The specific heat of water is 4.184 J/(g x
o
C) and of lead, 0.129 J/(g x oC).
A sample of silver with a mass of 98.2 g is heated to

a temperature of 402.9 K and placed in a container
of water at 298.1 K. The final temperature of the
silver and water is 326.3 K. What mass of water was
in the container? The specific heat of water is 4.184
J/(g x oC) and of silver, 0.235 J/(g x oC).
Calorimetry Review
• Way to determine heat transfer by placing
object in water and measuring the
temperature change.
• Most calorimetry problems are exothermic
-qsystem = +qsurroundings
A sample of silver with a mass of 98.2 g is heated to

a temperature of 402.9 K and placed in a container
of water at 298.1 K. The final temperature of the
silver and water is 326.3 K. What mass of water was
in the container? The specific heat of water is 4.184
J/(g x oC) and of silver, 0.235 J/(g x oC).
Enthalpy
Enthalpy is the heat content of a system at
constant pressure.
We cannot actually measure enthalpy.
What we can measure is the heat absorbed or
released in a chemical reaction (Change in
enthalpy)
∆H = Hproducts – Hreactants
Molar Enthalpy for a phase change:
The amount of heat that is released or absorbed during the phase change
of 1 mole of material
Remember, gas contains the most energy, solid the least.

– ΔH is negative when going from gas to liquid.
– ΔH is positive when going from solid to liquid.

Endothermic (Graph)
ΔH > 0
Enthalpy (heat) of reaction is positive.
Thermochemical Equation:
2 H2O (g) + 483.6 kJ  2H2 (g) + O2 (g)
Exothermic (Graph)
ΔH < 0
Enthalpy (heat) of reaction is negative.
Thermochemical Equation:
2 H2 (g) + O2 (g)  2H2O (g) + 483.6 kJ
Things to remember with ΔH
• The coefficients represent moles, meaning
we can have fractions if needed.
• Phases of the compounds are important
• The value of ΔH can be manipulated with

algebra.
– ie. Double the amount of reactants, double ΔH
For the equation:
C (s) + O2 (g)  CO2 (g) ΔH = -393.5 kJ
What is the ΔH for the reaction

2 CO2 (g)  2C (s) + 2O2 (g)
How much heat is evolved when 54.0 g glucose
(C6H12O6) are burned according to the following
equation? ∆Hcomb = - 2808 kJ/mol
C6H12O6 (s) + 12O2 (g)  6CO2 (g) + 6H2O (l)
Homework
• Pg 552
– #11, 12, 14
Hess’s Law:
The sum of the enthalpy changes for the individual
reactions is the enthalpy change for the final
reaction
Applying Hess’s Law
Calculate the energy change for the reaction that produces
SO3.
2S(s) + 3O2(g)  2SO3(g) ∆H = ?
a. S(s) + O2(g)  SO2(g) ∆H = - 297 kJ

b. 2SO3(g)  2SO2(g) + O2(g) ∆H = 198 kJ
Determine ∆H for the decomposition of H2O2.
2H2O2(l)  2H2O(l) + O2(g) ∆H = ?
a. 2H2(g) + O2(g)  2H2O(l) ∆H = - 572 kJ

b. H2(g) + O2(g)  H2O2(l) ∆H = - 188 kJ
Determine ∆H for the reaction.
5C (s) + 6H2 (g)  C5H12 (g) ∆H = ?
a. C (s) + O2 (g)  CO2 (g) ∆H = - 393.5 kJ

b. H2(g) + ½ O2(g)  H2O (l) ∆H = - 285.8 kJ
c. C5H12 (g) + 8 O2(g) 5 CO2 (g) + 6 H2O (l) ∆H = -3535.6 kJ
2 C (s)  2 H2O (g)  CH4 (g)  CO2(g)
Determine the standard enthalpy change for this reaction from the following
standard enthalpies of reaction :
(1) C(s)  H2O (g)  CO (g)  H2 (g) H  131.3 kJ
(2) CO (g)  H2O (g)  CO2 (g)  H2 (g) H  - 41.2 kJ
(3) CH4 (g)  H2O (g)  3 H2 (g)  CO (g) H  206.1 kJ
Standard Enthalpy (Heat) of Formation
• The change in enthalpy (heat) that
accompanies the formation of one mole of
the compound in its standard state from its
constituent elements in their standard states.
(1 atm, 25oC)
• Every free element in its standard state is

assigned a ∆Hfo of 0.0 kJ.
Short Way
Use standard heats of formation to determine the

enthalpy of reaction for…
Obtain ∆Hfo from Table A-14, p.862.
CH4 (g) + 2O2(g)  CO2(g) + 2H2O (l)
∆Hrxno = ∑∆Hfo(products) - ∑∆Hfo(reactants)

Use standard enthalpies of formation to calculate ∆Hrxno for
H2S(g) + 4F2(g)  2HF(g) + SF6(g) ∆Hrxno = ?
∆Hrxno = ∑∆Hfo(products) - ∑∆Hfo(reactants)

Use standard enthalpies of formation to calculate ∆Hrxno
for ….
SO3(g) + H2O(l)  H2SO4(aq)

• Entropy (S) is a measure of the disorder or
randomness of the particles that make up a
system.
• If system goes from organized to random

– ΔS is positive
• If system goes from random to organized

– ΔS is negative
Is ΔS is positive or negative?
• Water is boiled
• NH4Cl (s)  NH3 (g) + HCl (g)
• 2 Na (s) + Cl2 (g)  2NaCl (s)

Reaction Spontaneity
A spontaneous process is a physical or chemical
change that occurs with no outside intervention.
(Ex. Rust)
Fe + O2  Fe2O3 (rust)
Some spontaneous processes need energy to get

started and then they continue on their own
spontaneously.
CH4 (g) + 2O2(g)  CO2(g) + 2H2O(l)

• Both enthalpy and entropy play a role in
determining whether a chemical process
occurs spontaneously.
• Law of Disorder:
Spontaneous processes always proceed in
such a way that the entropy of the universe
increases.
Can we determine for sure if a reaction is
spontaneous?
ΔG0system = ΔHosystem – TΔSosystem
“H” is enthalpy.
“T” is temperature in kelvin
“S” is entropy
“G” is Gibbs free energy, the energy that is
available to do work.
• The sign of the free energy change of the

system tells you whether or not a reaction or
process is spontaneous.
• If the free energy is negative, the reaction is
spontaneous.
• If the free energy is positive, the reaction is
nonspontaneous.
Relating Enthalpy, Entropy, and Free-Energy
ΔH ΔS ΔG
Negative Positive Always negative

(exothermic) (more random) (spontaneous)
Negative Negative Negative at LOWER

(exothermic) (less random) temperatures
Positive Positive Negative at HIGHER

(endothermic) (more random) temperatures
Positive Negative Never negative

(endothermic) (less random) (non-spontaneous)

For a process, ΔHsystem = 145 kJ and ΔSsystem = 322

J/K. Is the process spontaneous at 382K?
Determine if each is spontaneous.
a) ΔHsystem = - 75.9 kJ, T = 273 K, ΔSsystem = 138 J/K
b) ΔHsystem = - 27.6 kJ, T = 535 K, ΔSsystem = - 55.2 J/K
c) ΔHsystem = 365 kJ, T = 388 K, ΔSsystem = - 55.2 J/K

Homework
• Pg 553
– #23 - 28

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Chapter 16 - Thermochemistry

There is an energy change that occurs with each chemical

Endothermic (Heat is taken in from the

Exothermic (Heat is released to the

1 Calorie = 1000 cal = 1 kcal = 4186 J

How many joules of energy will a 175 Calorie granola bar

• It is the amount of heat it takes to raise the temperature

Aluminum 0.897 J/(g x oC)

b. What is the specific heat of copper?

b. What is the specific heat of olive oil?

• A Calorimeter is used to measure the amount

How much heat is absorbed or released by the water?

If the final temperature of the gold is 67oC, what is the final

A sample of lead with a mass of 58.9 g is heated to a

A sample of silver with a mass of 98.2 g is heated to

• Most calorimetry problems are exothermic

A sample of silver with a mass of 98.2 g is heated to

Remember, gas contains the most energy, solid the least.

– ΔH is positive when going from solid to liquid.

• Phases of the compounds are important

• The value of ΔH can be manipulated with

What is the ΔH for the reaction

a. S(s) + O2(g)  SO2(g) ∆H = - 297 kJ

2H2O2(l)  2H2O(l) + O2(g) ∆H = ?

a. 2H2(g) + O2(g)  2H2O(l) ∆H = - 572 kJ

a. C (s) + O2 (g)  CO2 (g) ∆H = - 393.5 kJ

• Every free element in its standard state is

Use standard heats of formation to determine the

CH4 (g) + 2O2(g)  CO2(g) + 2H2O (l)

∆Hrxno = ∑∆Hfo(products) - ∑∆Hfo(reactants)

H2S(g) + 4F2(g)  2HF(g) + SF6(g) ∆Hrxno = ?

∆Hrxno = ∑∆Hfo(products) - ∑∆Hfo(reactants)

SO3(g) + H2O(l)  H2SO4(aq)

• If system goes from organized to random

• If system goes from random to organized

• NH4Cl (s)  NH3 (g) + HCl (g)

• 2 Na (s) + Cl2 (g)  2NaCl (s)

Some spontaneous processes need energy to get

CH4 (g) + 2O2(g)  CO2(g) + 2H2O(l)

ΔG0system = ΔHosystem – TΔSosystem

• The sign of the free energy change of the

Negative Positive Always negative

Negative Negative Negative at LOWER

Positive Positive Negative at HIGHER

Positive Negative Never negative

ΔG0system = ΔHosystem – TΔSosystem

For a process, ΔHsystem = 145 kJ and ΔSsystem = 322

b) ΔHsystem = - 27.6 kJ, T = 535 K, ΔSsystem = - 55.2 J/K

c) ΔHsystem = 365 kJ, T = 388 K, ΔSsystem = - 55.2 J/K

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