Thermochemistry

Dr. Jensen
CHM 111

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Learning Objectives
• Energy, Heat and Work
• Should be able to identify appropriate signs for q and w
• Should be able to calculate internal energy, given heat and work
• Energy and Enthalpy
• Should be able to calculate pressure-volume work
• Specific Heat
• Should be able to use specific heat to determine change in temperature
• Should be able to calculate heat required to change the temperature of a
substance
• Enthalpy in Chemical Reactions
• Should be able to calculate heat from a chemical reaction (stoichiometry)
• Should be able to calculate Enthalpy utilizing Hess’s Law
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Thermodynamics
• Thermodynamics is a branch of physics/chemistry that studies the
movement of heat between different objects. Thermodynamics
also studies the change in pressure and volume of objects (work).
• Thermodynamics is useful because it helps us understand how the
world of the very small atoms connects to the large scale world we
see everyday.

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 Energy, Heat and Work

• Should be able to identify appropriate signs for q and w

• Should be able to calculate internal energy, given heat and
work

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Energy, Heat and Work
• Energy is anything that has the capacity to do work or transfer
heat.
• Quantity an object or collection of objects can possess
• You can think of heat and work as the two different ways that an
object can exchange energy with other objects.
• either out of it, or into it
• Energy can be exchanged between objects through contact.
• collisions
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Units of Energy
• The amount of kinetic energy an object has is directly
proportional to its mass and velocity.
 KE = ½mv2
• When the mass is in kg and velocity in m/s, the unit for kinetic
energy is .
• One joule of energy is the amount of energy needed to move a 1-
kg mass at a speed of 1 m/s.
 1J=1
 Units of Energy
• One joule (J) is the amount of energy needed to move a 1-kg mass a
distance of 1 meter.
• 1 J = 1 N∙m = 1 kg∙m2/s2
• One calorie (cal) is the amount of energy needed to raise one gram
of water by 1 °C.
• 1 kcal = energy needed to raise 1000 g of water 1 °C
• food Calories = kcals

Energy Conversion Factors

1 calorie (cal) = 4.184 joules (J) (exact)
1 Calorie (Cal) = 1000 calories (cal)
1 kilowatt-hour (kWh) = 3.60 × 106 joules (J)
System and Surroundings
• We define the system as the
material or process that
contains the energy changes
we are studying.

• We define the surroundings

as everything else in the
universe.
• What we study is the
exchange of energy between
the system and the
surroundings
First Law of Thermodynamics
• Energy can move between a system and its surroundings.

• Some types of energy can be converted from one form to the other.

• The law of conservation of energy states that energy cannot be

created or destroyed, just transferred from one form to another.

• The first law of thermodynamics states that the energy of the

universe is constant.
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Energy Flow and Conservation of Energy
• Conservation of energy requires that the total energy change in
the system and the surroundings must be zero.

• DEnergyuniverse = 0 = DEnergysystem + DEnergysurroundings

• D is the symbol that is used to mean change.
• (final amount – initial amount)

• Energy output from fire is Energy input of water

• Total Net change of energy is 0
Internal Energy
• The internal energy is the total amount of kinetic and potential
energy a system possesses.
• The change in the internal energy of a system depends only on the
amount of energy in the system at the beginning and end.
• A state function is a mathematical function whose result
depends only on the initial and final conditions, not on the
process used.
• DE = Efinal – Einitial
• DEreaction = Eproducts – Ereactants
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 Energy Diagram

Internal Energy
initial
• High energy compounds like
pyrotechnic powder are made DE = –
up of compounds that when final
ignited give off energy and
form more stable (LOWER
Energy) products
 Energy Diagram

Internal Energy
final
• Ammonium Nitrate when energy added
dissolved in water absorbs DE = +
energy from the initial
surroundings
• System is the Cold pack
• Surrounding is the skin

• Energy (heat) Leaves the

skin and goes into the cold
pack
Energy Flow
• When energy flows out of a system, it must all flow into the
surroundings.
• When energy flows out of a system, DEsystem is negative (–).
• When energy flows into the surroundings,
• DEsurroundings is positive (+).
• therefore:
• –DEsystem = DEsurroundings
Energy Flow
• When energy flows into a system, it must all come from the
surroundings.
• When energy flows into a system, DEsystem is positive (+).
• When energy flows out of the surroundings, DEsurroundings is negative
(–).
• therefore:
DEsystem = –DEsurroundings
 Chemical Reaction Energy

Internal Energy
C(s), O2(g)
• In the reaction C(s) + O2(g) → CO2(g), there energy
energy
will be a net release of energy into the absorbed
released
surroundings. CO2(g) DErxn +
rxn = –
• −DEreaction = DEsurroundings
• In the reaction CO2(g) → C(s) + O2(g), there
will be an absorption of energy from the
surroundings into the reaction. Surroundings
• DEreaction = −DEsurroundings

System
C
CO+2O
→2 →
C +CO
O2
Work and Heat Flow
• Work, w, is the energy resulting from a force acting on an object
over a distance.
• The flow of energy that causes a temperature change in an object
or its surroundings is known as heat, q.
• Both work and heat can be exchanged between the system and
surroundings.

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Work Flow Between System and
Surroundings
Work done on the system
• w is positive
• If the system is a car, an
example is a person pushing
the car.
Work done by the system
• w is negative .
• If the system is a car, an
example is a moving car hitting
a person.
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Figure:
Work Flow Between the System and Surroundings

Positive (+) Negative (-)

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Heat Flow Between System and
Surroundings
Heat added to the system
• q is positive .
• An example is heat transferred
from a person’s hand to an ice
cube (the system).
Heat released by the system
• q is negative.
• An example is a bowl of cold
water (the system) left in the
freezer. Heat is transferred
from the bowl into the freezer
as the water cools and then
freezes.
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Figure:
Heat Transfer Between the System and Surroundings

Positive (+) Negative (-)

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Changes in Internal Energy, ΔE
**Note some books use U = E

• Changes in internal energy, ΔE, are more commonly measured

• When Efinal > Einitial, the internal energy of the system has increased
and is positive .

• When Efinal < Einitial, the internal energy of the system has decreased
and is negative .

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Table Summary
Expressions and Meanings of
Parameter Sign Physical Meaning
q + The system gains heat.
q – The system loses heat.
w + Work is done on the system.
w – Work is done by the system.
ΔE + The system gains internal energy.
ΔE – The system loses internal energy.
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Figure:
Changes in Work or Heat Affect the Internal Energy of the System.

DE DE

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Example 1
A reaction occurring in a flask releases 890 J of heat to the
surroundings and the gas produced performs 450 J of work on
the surroundings by pushing the piston upward.
The piston
is pushed
upward
a. Determine the signs
of q and w in this reaction.
b. Determine ΔE for this
reaction.

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Example 1 Solution
A reaction occurring in a flask releases 890 J of heat to the
surroundings and the gas produced performs 450 J of work on
the surroundings by pushing the piston upward.
The piston
is pushed
upward
a. and
b. Determine ΔE for this
reaction.

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Example 1 Solution
A reaction occurring in a flask releases 890 J of heat to the
surroundings and the gas produced performs 450 J of work on
the surroundings by pushing the piston upward.
The piston
is pushed
upward
a. and

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Energy and Enthalpy
• Should be able to calculate pressure-volume work

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Pressure–Volume Work
• PV work is work that is the result of a volume change against
an external pressure.
• When gases expand, DV is +, but the system is doing work on
the surroundings, so wgas is –.
• As long as the external pressure is kept constant,
–work = external pressure × change in volume
w = –PDV
• To convert the units to joules, use 101.3 J = 1 atm∙L.

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Example 2 : If a balloon is inflated from 0.100 L to 1.85 L against an external
pressure of 1.00 atm, how much work is done?
Given: V1 = 0.100 L, V2 = 1.85 L, P = 1.00 atm
Find: w, J
Conceptual
Plan: P, DV w

Relationships: 101.3 J = 1 atm∙L

Solution:

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Example 3:
A chemical reaction is performed in a flask that is sealed with a
piston. The initial volume of the system is 0.550 L and the final
volume is 0.375 L. The pressure remains constant at 1.00 atm.

a. Calculate the amount of work performed (in joules) during this

reaction.
b. Determine whether the piston moves upward or downward over
the course of this reaction.

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Example 3 Solution (1 of 3)
A chemical reaction is performed in a flask that is sealed with a
piston. The initial volume of the system is 0.550 L and the final
volume is 0.375 L. The pressure remains constant at 1.00 atm.

a. Calculate the amount of work performed (in joules) during this

reaction.
First, calculate

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Example 3 Solution (2 of 3)
A chemical reaction is performed in a flask that is sealed with a
piston. The initial volume of the system is 0.550 L and the final
volume is 0.375 L. The pressure remains constant at 1.00 atm.

a. Calculate the amount of work performed (in joules) during this

reaction.
Then calculate w.

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Example 3 Solution (3 of 3)
A chemical reaction is performed in a flask that is sealed with a
piston. The initial volume of the system is 0.550 L and the final
volume is 0.375 L. The pressure remains constant at 1.00 atm.

a. Calculate the amount of work performed (in joules) during this

reaction.
Finally, convert to J.

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Specific Heat
• Should be able to use specific heat to determine change in temperature
• Should be able to calculate heat required to change the temperature of a
substance

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Specific Heat
• In the absence of a phase change, the amount of heat required to
change the temperature of a substance is given by

• m is the mass of the substance, c is the specific heat of the

substance, and ΔT is the change in temperature in either degrees
Celsius or kelvins. 
• The specific heat, c, of a substance is the number of calories
required to raise exactly 1 g of the substance by exactly 1°C.
Typical units are .
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Table: Specific Heats of Selected Substances
Covalent Specific
Heat Metal
Specific
Heat Metal
Specific
Heat
Substance (J/g · °C) (J/g · °C) (J/g · °C)
CO2 0.852 Al 0.892 Pb 0.13
CO 1.04 Cr 0.45 Mg 1.0
H2 14.4 Co 0.46 Ag 0.24
N2 1.04 Cu 0.385 Na 0.293
O2 0.922 Au 0.129 Sn 0.22
Fe 0.442 Zn 0.388
H2O(g) 2.042
H2O(l) 4.184
H2O(s) 2.089

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Interpreting Specific Heat Values
• Substances with higher specific heat values resist temperature
changes more than substances with lower specific heat values.
• Examples
• Due to its high specific heat of 4.184 J/g · °C, water can absorb a
significant amount of heat without experiencing an increase in
temperature.

• Dry sand (the major component of sand, silicon dioxide, has a specific
heat of 1.0 J/g · °C) on a beach can be uncomfortably hot to walk on
barefoot during a summer afternoon, while the water is cool.

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Example 4 How much heat is absorbed by a copper penny
with mass 3.10 g whose temperature rises from –8.0 °C to
37.0 °C?
Sort Given: T1 = –8.0 °C, T2 = 37.0 °C, m = 3.10 g
information
Find: q, J
Strategize Conceptual Cs m, DT q
Plan:

Relationships: q = m ∙ Cs ∙ DT
Cs = 0.385 J/g (Table 6.4)
Follow the Solution:
conceptual plan
to solve the
problem.

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Example 5—Calculate the amount of heat released
when 7.40 g of water cools from 49° to 29 °C.
Sort information Given: T1 = 49 °C, T2 = 29 °C, m = 7.40 g
Find: q, J
Strategize Conceptual Cs m, DT q
Plan:

Relationships: q = m ∙ Cs ∙ DT
Cs = 4.18 J/gC (Table 6.4)
Follow the Solution:
conceptual plan
to solve the
problem

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Example 6:
Calculate the final temperature after 1485 J of energy is added to
16.7 g of water at 23.4°C.

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Example 6 Solution (1 of 2)
Calculate the final temperature after 1485 J of energy is added to
16.7 g of water at 23.4°C.

Rearrange the equation to solve for the temperature change.

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Example 6 Solution (2 of 2)
Calculate the final temperature after 1485 J of energy is added to
16.7 g of water at 23.4°C.

Now determine the final temperature.

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Enthalpy in Chemical Reactions
• Should be able to calculate heat from a chemical reaction (stoichiometry)
• Should be able to calculate Enthalpy utilizing Hess’s Law

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Heat at constant pressure - Enthalpy
• The change in enthalpy of a system, ΔH, is equal to the flow of heat
at constant pressure, qp, expressed as

• Endothermic reactions absorb heat from the surroundings and

have positive ΔH values, whereas exothermic reactions release heat
to the surroundings and have negative ΔH values.

• Usually DH and DE are similar in value; the difference is largest for

reactions that produce or use large quantities of gas.
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Endothermic and Exothermic Processes
• when heat is transferred from the surroundings to the system.
• Reactions that absorb heat from the surroundings are known
as endothermic processes.
• when heat is transferred from the system to the surroundings.
• Reactions that transfer heat to the surroundings are known
as exothermic processes.

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 Exothermic
• For an exothermic reaction, the
outside temperature rises due to
release of thermal energy.
• This extra thermal energy comes
from the conversion of some of
the chemical potential energy in
the reactants into kinetic energy
in the form of heat.
• The products of the reaction have
less chemical potential energy
than the reactants.
• The difference in energy is
released as heat. 54
 Endothermic
• In an endothermic reaction, the
surrounding temperature drops due
to absorption of some of its thermal
energy.
• The products of the reaction have
more chemical potential energy than
the reactants.
• To acquire this extra energy, some of
the thermal energy of the
surroundings is converted into
chemical potential energy stored in
the products.
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 Mass B
Mass A
MW MW

Balanced
Vol A M Equation M Vol B
(aq) Moles of A Moles of B (aq)

Av
o’ s# og
ad
r DH
gad ro
’s
o
Av #
HEAT
Particles Particles

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 Example 7 50g methane is burned How much Heat is
produced?

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

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

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

50 𝑔𝐶𝐻 4 1𝑚𝑜𝑙𝑒 − 891 𝐾𝐽

❑ 16 𝑔𝐶𝐻 4 1 𝑚𝑜𝑙𝑒 = -2784 KJ

Mass A MW DH
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Example 8 How much heat is evolved in the
complete combustion of 13.2 kg of C3H8(g)?
Given: 13.2 kg C3H8
Find: q, kJ/mol
Conceptual kg g mol kJ
Plan:

Relationships: 1 kg = 1000 g, 1 mol C3H8 = –2044 kJ, Molar Mass = 44.09 g/mol

Solution:

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Example 9 How much heat is evolved when a
0.483-g diamond is burned?
Given: 0.483 g C, DH = –395.4 kJ/mol C
Find: q, kJ/mol
Concept Plan: g mol kJ

Relationships: 1 mol C = −395.4 kJ, Molar Mass = 12.01 g/mol

Solution:

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Hess’s Law
• The enthalpy changes for some reactions are difficult to measure
directly.
• These can be calculated by manipulating the equations for other
reactions with known ΔH values.
• When chemical equations are added together to yield a different
chemical equation, the corresponding ΔH values are added to get
the ΔH for the desired equation.
• This principle is known as Hess’s law.

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Relationships Involving DHrxn - Hess’s Law

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Manipulating Chemical Equations: Rule 1
1. When an equation is reversed, the sign of its enthalpy
changes.

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Manipulating Chemical Equations: Rule 2
2. When the coefficients in an equation are multiplied or divided by
a factor, the enthalpy value is multiplied or divided by that same
factor.

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Manipulating Chemical Equations: Rule 3
3. When reactions are summed, the enthalpy of the overall reaction
is the sum of the enthalpies of the component reactions.

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Example 10 —Hess’s Law
Given the following information:
Cu(s) + Cl2(g)  CuCl2(s) DH° = −206 kJ
2 Cu(s) + Cl2(g)  2 CuCl(s) DH° = −36 kJ
Calculate the DH° for the reaction below:
Cu(s) + CuCl2(s)  2 CuCl(s) DH° = ? kJ

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Example 10—Hess’s Law
Given the following information:
Cu(s) + Cl2(g)  CuCl2(s) DH° = −206 kJ
2 Cu(s) + Cl2(g)  2 CuCl(s) DH° = −36 kJ
Calculate the DH° for the reaction below:
Cu(s) + CuCl2(s)  2 CuCl(s) DH° = ? kJ
CuCl2(s)  Cu(s) + Cl2(g) DH° = +206 kJ
2 Cu(s) + Cl2(g)  2 CuCl(s) DH° = −36 kJ
Cu(s) + CuCl2(s)  2 CuCl(s) DH° = +170. kJ

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 Example 11—Hess’s Law
Given the following information:
2 NO(g) + O2(g)  2 NO2(g) DH° = −116 kJ
2 N2(g) + 5 O2(g) + 2 H2O(l)  4 HNO3(aq) DH° = −256 kJ
N2(g) + O2(g)  2 NO(g) DH° = +183 kJ
Calculate the DH° for the reaction below:
3 NO2(g) + H2O(l)  2 HNO3(aq) + NO(g) DH° = ?
[2[3
NONO2(g) 
2(g) 2 NO(g)
3 NO(g) +O (g)]O×2(g)]
+21.5 1.5 DH°
DH° = 1.5(+116
= (+174 kJ) kJ)
[2[1
N2N(g) + 5+ O
2(g) 2(g)
2.5 O2+(g)
2H+ 21O(l)  4
H2O(l) HNO 3(aq)]
2 HNO × 0.5DH°
3(aq)] DH° = 0.5(−256
= (−128 kJ) kJ)
[2[2
NO(g)
NO(g)  N2N (g) +O
2(g) (g)]
+2O 2(g)] DH°
DH°= −183 kJ kJ)
= (−183
3 NO2(g) + H2O(l)  2 HNO3(aq) + NO(g) DH° = −137 kJ

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Formation Reactions
• reactions of elements in their standard state to form 1 mole of a
pure compound
• If you are not sure what the standard state of an element is, find
the form in Appendix IIB that has a
• DHf° = 0.
• Since the definition requires 1 mole of compound be made, the
coefficients of the reactants may be fractions.

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Standard Conditions
• The standard state is the state of a material at a defined set of conditions.
• pure gas at exactly 1 atm pressure
• pure solid or liquid in its most stable form at exactly 1 atm pressure and temperature of
interest
• usually 25 °C
• substance in a solution with concentration 1 M
• The standard enthalpy change, DH°, is the enthalpy change when all
reactants and products are in their standard states.
• The standard enthalpy of formation, DHf°, is the enthalpy change for the
reaction forming 1 mole of a pure compound from its constituent elements.
• The elements must be in their standard states.
• The DHf° for a pure element in its standard state = 0 kJ/mol.
• by definition

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