Thermochemistry

Heatand
Chemical Change

1
Thermochemistry

The study of energy or heat

flow that accompanies a
chemical reaction and/or
physical transformations

2
TEMPERATURE VS. HEAT

Temperature is a measure of the

average kinetic energy of the
molecules

Heat is the sum total amount of

energy of all the molecules

3
Which is at a higher temperature?
4
Which possesses more heat energy?
5
heat energy = specific heat x mass x change
in temperature

Q = s∙m∙T 6
 Specific Heat Capacity:
The amount of heat energy
required to raise the
temperature of 1 gram of a
substance by 1 °C
Energy is measured in Joules ( J )

Symbol = s
Unit = J/g
7
Specific Heat Capacities :
Substance J/g°C
H2O (l) 4.18
Al 0.89
Fe 0.45
Hg 0.14
C 0.71
ethanol 2.44

8
Specific Heat Capacity of Water:

4.184 J/gºC
You must memorize this number!

9
Specific Heat Capacities :
The higher the specific heat capacity,
the more energy it takes to raise the
Temperature of a substance

How does water’s high specific heat

capacity make it such a valuable
resource to living things?

10
You place 10 gram samples of both
Al and Fe in a hot oven for a short
period of time….

0.89 J/g0C 0.45

J/gC
Al Fe

Which substance will heat up the

fastest?
11
You place 10 gram samples of both
Al and Fe in a hot oven for a short
period of time….

0.89 J/gC 0.45

J/gC
Al Fe

Which substance has to absorb

more heat energy to warm up?
12
You now place both the Al and Fe in
the same oven and let them sit
overnight…..
0.89 0.45
J/gC J/gC
Al Fe

13
You now place both the Al and Fe in
the same oven and let them sit
overnight…..
0.89 0.45
J/gC J/gC
Al Fe
Which substance will be at the higher
temperature at the end of this time?
14
You now place both the Al and Fe in
a boiling water bath and let them
sit overnight…..
0.89 0.45
J/gC J/gC
Al Fe
Which substance has absorbed more
heat energy to get to this temperature?
Let’s do a calculation!
15
 Q = s∙m∙T
QAl = 0.89∙10∙100 = 890 QFe = 0.45∙10∙100 = 450

0.89 0.45
J/gC J/gC
Al Fe
Which substance has absorbed more
heat energy to get to this temperature?
16
 H2O (l) 4.184 J/g°C
Ethano 2.44 J/g°C
l
Which substance would be a better coolant
in a car’s radiator? Why?

17
Calculations with Specific Heat
Q = smT
Q= Heat energy(J)
s= specific heat (J/g·Cº)
m= mass of sample (g)
T = change in temperature (ºC)
(Tfinal – Tinitial)

J = Joules 18
 Calculations with Specific Heat
Example 1: How much heat is absorbed when the
temperature of a 125 g piece of aluminum increases from
35ºC to 65ºC. The specific heat capacity of Aluminum is
0.90 J/g·ºC.
Q = smT
Q= ?J
s = 0.90 J/g·Cº
m = 125 g
T = change in temperature (ºC)
(Tfinal – Tinitial)

Q = 0.90 J x 125g x 30oC =

3375 J
g· oC 1 1 3400 J (2 sf)
19
 Calculations with Specific Heat
Example 2: The temperature of a 95.4g piece of
copper increases from 25.0ºC to 48.0ºC when the
copper absorbs 849 J of heat. What is the specific
heat of copper?
Q = smT s = Q
Q= 849 J mT
s= ?
m = 95.4 g s = 849 J
T = 23.0ºC)
(Tfinal – Tinitial
)
95.4 g ∙ 23.0 o
C
s = .387 J
g ∙ oC 20
Practice Exercises:
1. How many kilojoules of heat are absorbed when
1000g of water is heated from 18oC to 85oC?

2. A 40.5g sample of alloy is heated to 90.8oC and

then placed in water, where it coolsto 23.54oC.
The amount of heat lost by the alloy is 865 J. What is
the specific heat of the alloy?
3. A 7.0-gram metal sample absorbed 211J of heat as it
was heated from 28 o C to 85 o C. What is the specific
heat of the metal?

21
Calorimetry:
• The measurement of heat energy
transferred during a physical or
chemical process

22
Calorimetry:
• The measurement of heat energy
transferred during a physical or
chemical process
• The heat energy that is gained or
lost is absorbed or released into
water in a calorimeter

23
 Calorimetry:
• The measurement of heat energy
transferred during a physical or
chemical process
• The heat energy that is gained or
lost is absorbed or released into
water in a calorimeter
• Heat lost by process = heat gained
by water
24
 Calorimetry:
Heat lost by metal = heat gained by water

smetalmmetalTmetal = swatermwaterTwater

smmmTm = swmwTw
Metal water
Specific heat x mass x temp change = Specific heat x mass x temp change

25
Calorimetry Experiment

26
Heat lost = Heat Gained Calculations
smmmTm = swmwTw
Example 1: A piece of metal with a mass of 678 g is heated to 99.8°C
and dropped into 250.0 mL of water at 26.0°C. The final
temperature of the system is 27.1°C. What is the specific heat of
the metal?

First determine heat Now determine specific heat of metal

gained by water
Q = 4.184 ∙ 250.0g ∙ 1.1 =
Q = - 1150J s = Q
Q = 1150J
s = 4.184 J/g·Cº s = ? J/g·Cº mT
m = 250.0 g m = 678 g s = -1150 J
T = 1.1 ºC T = -72.7 ºC 678 g ∙ -72.7oC
(Tfinal – Tinitial) (Tfinal – Tinitial) s = .0233 J
g ∙ oC 27
Heat lost = Heat Gained Calculations
smmmTm = swmwTw
Example 2: A piece of metal is heated to 76.8°C and
dropped into 75.0 mL of water at 22.0°C.The final
temperature of the system is 27.1°C. The specific heat of
the metal is .98 J/g°C. What is the mass of the metal piece?
Metal Water – do first!
Q = -1600J Q = 4.184 · 75.0 · 5.1 = 1600J
s = .98 J/g·Cº s = 4.184 J/g·Cº
m= ? g m = 75.0 g
T = 27.1 - 76.8 = -49.7 ºC T = 27.1- 22.0 = 5.1 ºC
(Tfinal – Tinitial) (Tfinal – Tinitial)
m = -1600
(.98) · (-49.7) = 32.85 so 33g
28
Sample exercises:
1. An iron bar at 65.5°C is placed in a beaker of water at 25.0
°C. If the mass of the water is 65.0 g and the final
temperature at thermal equilibrium is 32.5 °C. What is the
mass of the iron bar? The specific heat capacity of water is
4.184 J/g °C.
2. A 10-g solid was heated in a test tube to 100o C in boiling
water and added to the coffee cup calorimeter with 50 g of
water. The water temperature increased from 25.1 to 28o C.
What is the specific heat of the solid?
3. A metal weighing 4.82 g was heated to 115.0 oC and put into
35 mL of water of temperature 28.7 oC. The metal and water
were allowed to come to an equilibrium temperature,
determined to be 34.5 O C. Assuming no heat was lost to the
environment, calculate the specific heat of the metal. 29
 Changes in Heat Energy within a
Chemical Reaction
• Energy can be gained or lost in the form
of heat during a chemical reaction
• When heat energy is gained (or absorbed),
a reaction is called endothermic
• When heat energy is lost (or released), a
reaction is called exothermic
• The change in heat is represented by the
symbol H
30
 Exothermic
Surroundings

Heat Released

Energy
System
H= negative
31
 Exothermic Reactions
An exothermic reaction will feel warm or
hot to touch because you feel the heat
being released from the reaction!

32
CH 4 + 2O 2  CO 2+ 2H 2 O + Heat

Reactants
CH 4 + 2O 2
Heat
Energy

Products
CO2 + 2 H
2O
EXOTHERMIC  H = negative
33
 Endothermic
Surroundings

Heat Absorbed

Energy
System
H= positive
34
 Endothermic Reactions
An endothermic reaction will feel cool or
cold to the touch because the heat from your
hand is being absorbed by the reaction!

35
 N 2 + O 2 + h ea t  2 N
O Products
2N
O
Energy

Reactants
Heat
N2 +
O2
ENDOTHERMIC H = positive36
 Change in Energy (Heat)
H
The change in heat energy ( H) in a
chemical reaction is called enthalpy

 H = negative (-) = exothermic

H = positive (+) = endothermic

H is expressed in kJ (kilojoules)
37
 Signs of q(heat absorbed or released) and
w(performed by or done on the system)
Heat added to the system Heat evolved by the system

(+q) System (-q)

Work done on the system Work done by the system

(+w) (-w)

SURROUNDINGS

E= q+w
38
• q and w are positive (+) when heat or work
enters the system from the surroundings, i.e., heat
is absorbed by the system and work is done on the
system
• q and w are negative (-) when heat or work
transfers from the system to the surroundings, i.e.,
heat is evolved and work is done by the system
• If both q and w are (+), sign of E is also (+);
internal energy increases
• If both q and w are (-),sign of E is also (-);
internal energy decreases
• If q is (+) and w is (-), or if q is (-) and w is (+),
sign of E depends on the magnitude of q and w
39
Sample Problem:

1. Calculate E if 100 kJ of heat energy is absorbed

by the system and 30 kJ of work is done on the
surroundings.
2. Find E
a. when 175 J of work done on a system that
evolves 50 J of heat to the surroundings
b. when a gas absorbs 28 kJ of heat and has 13
kJ of work done on it
3. What is the energy change of a system as it does
12 J of work and absorbed 27 J of heat?
40
Calculations Using
Heat Energy

41
 2 S + 3 O2  2 SO3 H = -791.4 kJ

Example 1: How much heat will be released

when 3.000 moles of Sulfur react with excess
O2 in the reaction above?
3 mol S -791.4 kJ = -1187 kJ
1 2 mol S

Is the reaction exothermic or endothermic? How do you know?

42
 H2 + Br2  2 HBr H = 72.80 kJ

2. How much heat will be absorbed

when 38.2 g of bromine reacts with
excess H2 in the reaction above?

Is the reaction exothermic or endothermic? 43

 H2 + Br2  2 HBr H = 72.80 kJ

How much heat will be absorbed when

38.2 g of bromine reacts with excess H2
in the reaction above?

38.2 g Br2 1 mol Br2 72.80 kJ

1 159.80 g Br2 1 mol Br2

= 17.4 kJ of heat energy absorbed

Is the reaction exothermic or endothermic? 44
 HESS’S LAW
(Hess’s Law of Constant
Heat Summation)

45
Hess’s Law

• When chemical equations are combined

algebraically, their enthalpies can be
combined in exactly the same way.
• It allows us to combine equations to
generate new chemical reactions whose
enthalpy changes can be calculated,
rather than directly measured.

46
 HESS’S LAW
• Sometimes reactions can occur in steps
rather than as single reaction
Example:
2C + H2 ---> C2H2
This reaction actually occurs in 3 steps:
C2H2 + 5/2 O2 ---> 2CO2 + H2O
C + O2 ---> CO2
H2 + ½ O2 ---> H2O
47
 HESS’S LAW
• Regardless of the number of steps of a
reaction, the total enthalpy change for the
reaction is the sum of all changes.

2C(s) + H2(g) ---> C2H2(g) H = ??

C2H2 + 5/2 O2 ---> 2CO2 + H2O H = -1299.5 kJ

C + O2 ---> CO2 H = -393.5 kJ

H2 + ½ O2 ---> H2O H = -285.8 kJ
48
 HESS’S LAW
Unfortunately, it is not as simple as just adding up all the
Enthalpies. We must manipulate the various steps to the
reaction until each matches the final reaction exactly.
2C(s) + H2(g) ---> C2H2(g) H = ??

C2H2 + 5/2 O2 ---> 2CO2 + H2O H = -1299.5 kJ

C + O2 ---> CO2 H = -393.5 kJ

H2 + ½ O2 ---> H2O H = -285.8 kJ
Which equation needs to be flipped? What is its new H value?

49
Steps to Solving Hess’ Law Problems
1. Circle the chemical formulas of interest in each step
equation
2. Flip the step equations so all reactants and products are
in the same locations as in the reaction of interest.
Remember to change the sign of H when you flip the
equation.
3. Multiply step equations so coefficients match the
equation of interest. Remember to multiply H also.
4. Cancel out chemical formulas that appear in both the
reactant and product sides of the step equations.
5. Sum all H values of the step equations.
50
• Let’s do an example together
Given the following data:
N2 + 2O2 ---> N2O4 H = 9.6 kJ
2NO2 ---> N2O4 H = -58.2 kJ

Calculate H for the reaction

2NO2  N2 + 2O2

51
• Let’s do an example together:
Given the following data:
OF2 + H2O ---> O2 + 2HF H = -277 kJ X2

SF4 + 2H2O ---> SO2 + 4HF H = 828 kJ flip

S + O2 ---> SO2 H = -297 kJ X2

Calculate H for the reaction

2S + 2OF2  SO2 + SF4 H = -1976 kJ
2OF2 + 2H2O ---> 2O2 + 4HF H = -554 kJ (x2)
SO2 + 4HF ---> SF4 + 2H2O H = -828 kJ
2S + 2O2 ---> 2SO2 H = -594 kJ (x2)
H = -1976 kJ
52
Sample problem:

Given the following data:

C + O2 CO2 H0= -393.5kJ
H2 + 1/2O2 H2O H0= -285.8 kJ
CH4 + 2O2 CO2 + 2H2O H0= -890.4 kJ

Calculate the enthalpy change for the ff. reactions

C + 2H2 CH4 H=?

53
Hess’s Law
The enthalpy change of a physical or
chemical process is independent of the
pathway of the process and the number
of intermediate steps in the process.

Start Finish

Either way, you get to the finish. 54

Hess’s law allows you to determine the
energy of chemical reaction without directly
measuring it.

The enthalpy change of a chemical process is

equal to the sum of the enthalpy changes of
all the individual steps that make up the
process.

55
 Determine the heat of reaction for the reaction:
4NH3(g) + 5O2(g)  4NO(g) + 6H2O(g)

Using the following sets of reactions:

N2(g) + O2(g)  2NO(g) H = 180.6 kJ

N2(g) + 3H2(g)  2NH3(g) H = -91.8 kJ

2H2(g) + O2(g)  2H2O(g) H = -483.7 kJ

Hint: The three reactions must be algebraically

manipulated to add up to the desired reaction.
and.. the H values must be treated accordingly. 56
Goal: 4NH3(g) + 5O2(g)  4NO(g) + 6H2O(g)
Using the following sets of reactions:
N2(g) + O2(g)  2NO(g) H = 180.6 kJ

N2(g) + 3H2(g)  2NH3(g) H = -91.8 kJ

2H2(g) + O2(g)  2H2O(g) H = -483.7 kJ

NH3: Reverse and x 2 4NH3  2N2 + 6H2 H = +183.6 kJ

O2 : Found in more than one place, SKIP IT (its hard).
NO: x2 2N2 + 2O2  4NO H = 361.2 kJ
H2O: x3 6H2 + 3O2  6H2O H = -1451.1 kJ

57
 Goal: 4NH3(g) + 5O2(g)  4NO(g) + 6H2O(g)

NH3: Reverse and x2 4NH3  2N2 + 6H2 H = +183.6 kJ

O2 : Found in more than one place, SKIP IT.
NO: x2 2N2 + 2O2  4NO H = 361.2 kJ
H2O: x3 6H2 + 3O2  6H2O H = -1451.1 kJ

Cancel terms and take sum.

4NH3 + 5O2  4NO + 6H2O H = -906.3 kJ

Is the reaction endothermic or exothermic?

58
Determine the heat of reaction for the reaction:

C2H4(g) + H2(g)  C2H6(g)

Use the following reactions:

C2H4(g) + 3O2(g)  2CO2(g) + 2H2O(l) H = -1401 kJ

C2H6(g) + 7/2O2(g)  2CO2(g) + 3H2O(l) H = -1550 kJ

H2(g) + 1/2O2(g)  H2O(l) H = -286 kJ

Consult your neighbor if necessary.

59
 Determine the heat of reaction for the reaction:

Goal: C2H4(g) + H2(g)  C2H6(g) H = ?

Use the following reactions:

C2H4(g) + 3O2(g)  2CO2(g) + 2H2O(l) H = -1401 kJ

C2H6(g) + 7/2O2(g)  2CO2(g) + 3H2O(l) H = -1550 kJ

H2(g) + 1/2O2(g)  H2O(l) H = -286 kJ

C2H4(g) :use 1 as is C2H4(g) + 3O2(g)  2CO2(g) + 2H2O(l) H = -1401 kJ
H2(g) :# 3 as is H2(g) + 1/2O2(g)  H2O(l) H = -286 kJ
C2H6(g) : rev #2 2CO2(g) + 3H2O(l)  C2H6(g) + 7/2O2(g) H = +1550 kJ

C2H4(g) + H2(g)  C2H6(g) H = -137 kJ

60
Where do the reference equations come from?

Many can be determined through calorimetry.

ie. combustion reactions

Another type of reference equation is called

standard enthalpies of
formation.
61
 Standard Enthalpies of formation:
The standard enthalpy of formation is a measure of the energy
released or consumed when one mole of a substance is created
under standard conditions from its pure elements.

The symbol of the standard enthalpy of formation is ΔHof.

Δ = A change in enthalpy
o
= A degree signifies that it's a standard enthalpy change.
f = The f indicates that the substance is formed from its elements

An important point to be made about the standard enthalpy

of formation is that when a pure element is in its standard
form its standard enthalpy formation is zero. 62
The equation for the standard enthalpy change
of formation, shown below, is commonly used:

ΔHoreaction=∑nΔHof(products)−∑nΔHof(Reactants)

This equation essentially states that the

standard enthalpy change of formation is equal
to the sum of the standard enthalpies of
formation of the products minus the sum of
the standard enthalpies of formation of the
reactants.
63
Given a simple chemical equation with the variables A, B and C representing
different compounds:
A+B⇋C
and the standard enthalpy of formation values:
• ΔHfo[A] = 433 KJ/mol
• ΔHfo[B] = -256 KJ/mol
• ΔHfo[C] = 523 KJ/mol

the equation for the standard enthalpy change of formation is as follows:

ΔHreactiono = ΔHfo[C] - (ΔHfo[A] + ΔHfo[B])

ΔHreactiono = (1 mol)(523 kJ/mol) - ((1 mol)(433 kJ/mol) + (1 mol)(-256 kJ/mol))

Because there is one mole each of A, B and C, the standard enthalpy of

formation of each reactant and product is multiplied by 1 mole, which
eliminates the mol denominator:
ΔHreactiono = 346 kJ

The result is 346 kJ, which is the standard enthalpy change of formation for the
64
creation of variable "C".
EXAMPLE:
Calculate the ΔHreactiono for the formation of NO2(g).
NO2(g) is formed from the combination of NO(g) and O 2(g) in the following
reaction:
2NO(g)+O2(g)⇋2NO2(g)
To find the ΔHreactiono, use the formula for the standard enthalpy change of
formation:
ΔHoreaction=∑ΔHof(products)−∑ΔHof(Reactants)
The relevant standard enthalpy of formation values from the data table are as
follows:
• O2(g): 0 kJ/mol
• NO(g): 90.25 kJ/mol
• NO2(g): 33.18 kJ/mol
Plugging these values into the formula above gives the following:
ΔHreactiono= (2 mol)(33.18 kJ/mol) - ((2 mol)(90.25 kJ/mol) + (1 mol)(0 kJ/mol))
ΔHreactiono =-114.14kJ
65
Determining Enthalpies of Reaction from Standard Enthalpies of Formation

Example

Calculate DH° for the following reaction:

2Na(s) + 2H2O(l) → 2NaOH(aq) + H2(g)

Given the following information:

DHf° (kJ/mol)
Na(s) 0
H2O(l) –286
NaOH(aq) –470
H2(g) 0

[2(–470) + 0] – [0 + 2(–286)] = –368 kJ DH = –368 kJ

66
66
Thermodynamic Quantities of Selected Substances @ 298.15 K

67
67
Determining Enthalpies of Reaction from Standard Enthalpies of Formation

Learning Check

1. Calculate DH° for the following reaction:

4 NH3 (g) + 7O2(g) → 4 NO2(g) + 6H2O(l)

Use the Table on the left side side.

68
68
2.Using the standard molar enthalpies of formation given,
calculate the standard enthalpy of reaction for the
combustion of propane (C3H8) into a carbon and water
C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(g)

SUBSTANCE C3H8(g) O2(g) CO2(g) H2O(g)

H0f (kJ/mol) -104.0 0 -393.5 -241.8

69
States of Matter
Phase Changes, Heat of Fusion,
and Heat of Vaporization

70
Phases of Matter: (review)
Solid
matter that has definite volume and definite shape

Liquid
matter that has definite volume but indefinite
shape

Gas
matter that has indefinite volume and indefinite
shape

71
Phase Change Descriptions:

Melting
the change from solid to liquid.
Freezing
the change from liquid to solid.
Evaporation (vaporization)
the change from liquid to gas .
Condensation
the change from gas to liquid .
Sublimation
the change from solid to gas .
Deposition
the change from gas to solid .

72
Changes of State

73
 Phase Change Diagram (Heating/Cooling Curve)

condensing
Boiling
Point evaporating

Melting freezing
Point melting

74
•Heat of fusion: (Hfus)
the energy absorbed to change one
mole of a substance from a solid to
a liquid. (melting)
• Heat of vaporization: (Hvap)
the energy absorbed to change one
mole of a substance from liquid to
gas. (vaporizing)

75
• NO TEMPERATURE CHANGE
OCCURS DURING A PHASE
CHANGE!

76
 Hvap

condensing

evaporating

Hfus
freezing

melting

77
• When moving UP the curve, the
Hfus and Hvap will be POSITIVE
(+) because they are endothermic
processes
• When moving DOWN the curve,
the Hfus and Hvap will be
NEGATIVE (-) because they are
exothermic processes

78
 Hvap
Exothermic
H = (-) condensing

evaporating

Hfus Endothermic
freezing
H = (+)

melting

79
 Calculations with Phase Changes
Example 1: How much energy would it take to completely
melt a 7.20 mol sample of ice at 0°C? The heat of fusion
(Hfus) of H2O is 6.02 kJ/mol.

7.20 mol H2O 6.02 kJ

= 43.3 kJ
1 1 mol H2O

80
• Calculations with Phase Changes
Example 2: How much energy would it take to completely
melt a 15.0 g sample of ice at 0°C? The heat of fusion (Hfus)
of H2O is 6.02 kJ/mol.

What must we do first?

15.0g H20 1 mol H20 6.02kJ

= 4.96kJ
1 18.20g H20 1 mol H20

81
• Calculations with Phase Changes
Example 3: How much energy would be released when .456 g
of water vapor (gas) at 100°C condense completely? The heat
of vaporization (Hvap) of H2O is 40.7 kJ/mol.

.456g H20 1 mol H20 40.7kJ

= 1.02kJ
1 18.20g H20 1 mol H20

82