Calorimetry

Burning of a Match

System Surroundings
Potential energy

(Reactants)
D(PE) Energy released to the surrounding as heat

(Products)

Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 293

 Conservation of Energy
in a Chemical Reaction
In this example, the energy
Endothermic
of the reactants
Reaction
and products increases,
while the energy of the surroundings decreases.
Reactant + Energy Product
In every case, however, the total energy does not change.

Surroundings

Surroundings
Energy

System

System

Before After
Myers, Oldham, Tocci, Chemistry, 2004, page 41 reaction reaction
 Conservation of Energy
in a Chemical Reaction
In this example, the energy
Exothermic
of the reactants
Reactionand products decreases,
while the energy of the surroundings increases.
Reactant Product + Energy
In every case, however, the total energy does not change.

Surroundings Surroundings
Energy

System
System

Before After
Myers, Oldham, Tocci, Chemistry, 2004, page 41 reaction reaction
 Direction of Heat Flow

Surroundings

ENDOthermic EXOthermic
qsys > 0 qsys < 0
System

H2O(s) + heat  H2O(l) H2O(l)  H2O(s) + heat

melting freezing
System

Kotz, Purcell, Chemistry & Chemical Reactivity 1991, page 207

 Caloric Values
Food joules/grams calories/gram Calories/gram
Protein 17 000 4000 4

Fat 38 000 9000 9

Carbohydrates 17 000 4000 4

1calories = 4.184 joules 1000 calories = 1 Calorie

"science" "food"

Smoot, Smith, Price, Chemistry A Modern Course, 1990, page 51

Experimental Determination of Specific Heat of a Metal

Typical apparatus used in this activity include a boiler (such as large glass
beaker), a heat source (Bunsen burner or hot plate), a stand or tripod for
the boiler, a calorimeter, thermometers, samples (typically samples of
copper, aluminum, zinc, tin, or lead), tongs (or forceps or string) to handle
samples, and a balance.
 Thermometer

A Coffee Cup
Calorimeter
Styrofoam
cover

Styrofoam
cups

Stirrer

Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 302

 Bomb Calorimeter

thermometer

stirrer

full of water

ignition wire

steel “bomb”

sample
 oxygen supply thermometer
ignition
wires
stirrer
magnifying
eyepiece

insulating
jacket

air space
bucket

heater crucible
water

ignition coil sample steel bomb

1997 Encyclopedia Britanica, Inc.

A Bomb Calorimeter
Causes of Change - Calorimetry

Outline

Keys
Keys

http://www.unit5.org/chemistry/Matter.html
 Heating Curves

140
120
Gas - KE 
100
80
Temperature (oC)

60 Boiling - PE 
40
20 Liquid - KE 
0
-20 Melting - PE 
-40
-60
Solid - KE 
-80
-100
Time
 Heating Curves
• Temperature Change
– change in KE (molecular motion)
– depends on heat capacity

• Heat Capacity
– energy required to raise the temp of 1 gram of a
substance by 1°C
– “Volcano” clip -
– water has a very high heat capacity

Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem

 Heating Curves
• Phase Change
– change in PE (molecular arrangement)
– temp remains constant

• Heat of Fusion (Hfus)

– energy required to melt 1 gram of a substance at its
m.p.

Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem

 Heating Curves
• Heat of Vaporization (Hvap)
– energy required to boil 1 gram of a substance at its
b.p.
– usually larger than Hfus…why?

• EX: sweating,
steam burns, the
drinking bird

Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem

 Phase Diagrams
• Show the phases of a substance at different
temps and pressures.

Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem

 Humor
A small piece of ice which lived in a test tube
fell in love with a Bunsen burner.
“Bunsen! My flame! I melt whenever I see
you” said the ice.
The Bunsen burner replied” “It’s just a
phase you’re going through”.
 Heating Curve for Water
(Phase Diagram)
F
140 Heat = m x Cvap
120 Cv = 2256 J/g
BP D E
100 Heat = m x Cfus
Cf = 333 J/g
80 Heat = m x DT x Cp, gas
Temperature (oC)

60 Cp (steam) = 1.87 J/goC

40
Heat = m x DT x Cp, liquid
20 Cp = 4.184 J/goC
MP B
0 C

-20
-40
-60 Heat = m x DT x Cp, solid AB warm ice
BC melt ice (solid  liquid)
Cp (ice) = 2.077 J/goC CD warm water
-80 A
DE
ED
boil water (liquid  gas)
condense steam (gas  liquid)
EF superheat steam
-100
Heat
 Calculating Energy Changes -
Heating Curve for Water

140 DH = mol x DHvap

120 DH = mol x DHfus
100
80
Temperature (oC)

60 Heat = mass x Dt x Cp, gas

40
20 Heat = mass x Dt x Cp, liquid
0
-20
-40
-60
-80 Heat = mass x Dt x Cp, solid
-100
Time
Equal Masses of Hot and Cold Water

Thin metal wall

Insulated box Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 291
Water Molecules in Hot and Cold Water

Hot water Cold Water

90 oC 10 oC
Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 291
 Water Molecules in the same
temperature water

Water Water
(50 oC)
Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 291
(50 oC)
 Heat Transfer

Surroundings Final
Block “A” Block “B” Temperature
SYSTEM
20 g (40oC) 20 g (20oC) 30oC

Al Al  20 g  40o C   20 g  20o C  30o C

(20 g  20 g)

m = 20 g m = 20 g What will be the final temperature

T = 40oC T = 20oC of the system ?

a) 60oC b) 30oC c) 20oC d) ?

Assume NO heat energy is “lost” to the surroundings from the system.

? Heat Transfer

Surroundings Final
Block “A” Block “B” Temperature
SYSTEM
20 g (40oC) 20 g (20oC) 30.0oC
20 g (40oC) 10 g (20oC) 33.3oC

Al  20 g  40o C  10 g  20o C  33. 3 o C

Al (20 g  10 g)

m = 20 g m = 10 g What will be the final temperature

T = 40oC T = 20oC of the system ?

a) 60oC b) 30oC c) 20oC d) ?

Assume NO heat energy is “lost” to the surroundings from the system.

 Heat Transfer

Surroundings Final
Block “A” Block “B” Temperature
SYSTEM
20 g (40oC) 20 g (20oC) 30.0oC
20 g (40oC) 10 g (20oC) 33.3oC
20 g (20oC) 10 g (40oC) 26.7oC
Al
Al  20 g  20 C  10 g  40 C  26.6 C
o o
o

(20 g  10 g)
m = 20 g m = 10 g
T = 20oC T = 40oC

Assume NO heat energy is “lost” to the surroundings from the system.

 Heat Transfer

Surroundings Final
Block “A” Block “B” Temperature
SYSTEM
20 g (40oC) 20 g (20oC) 30.0oC
20 g (40oC) 10 g (20oC) 33.3oC
20 g (20oC) 10 g (40oC) 26.7oC

Ag  75 g  25o C   30 g 100 o C  46o C

H2O
(75 g  30 g)
m = 75 g m = 30 g
T = 25oC T = 100oC Real Final Temperature = 26.7oC
Why?

We’ve been assuming ALL materials

transfer heat equally well.
 Specific Heat
• Water and silver do not transfer heat equally well.
Water has a specific heat Cp = 4.184 J/goC
Silver has a specific heat Cp = 0.235 J/goC

• What does that mean?

It requires 4.184 Joules of energy to heat 1 gram of water 1oC
and only 0.235 Joules of energy to heat 1 gram of silver 1oC.

• Law of Conservation of Energy…

In our situation (silver is “hot” and water is “cold”)…
this means water heats up slowly and requires a lot of energy

whereas silver will cool off quickly and not release much energy.

• Lets look at the math!

Specific Heat

The amount of heat required to raise the temperature

of one gram of substance by one degree Celsius.
Calculations involving Specific Heat
q
c  
p
m T
OR q  c m  T
p

cp = Specific Heat
q = Heat lost or gained
T = Temperature change
m = Mass
Table of Specific Heats
Specific Heats of Some Common
Substances at 298.15 K
Substance Specific heat J/(g.K)
Water (l) 4.18
Water (s) 2.06
Water (g) 1.87
Ammonia (g) 2.09
Benzene (l) 1.74
Ethanol (l) 2.44
Ethanol (g) 1.42
Aluminum (s) 0.897
Calcium (s) 0.647
Carbon, graphite (s) 0.709
Copper (s) 0.385
Gold (s) 0.129
Iron (s) 0.449
Mercury (l) 0.140
Lead (s) 0.129
 Latent Heat of Phase Change

Molar Heat of Fusion

The energy that must be absorbed in order
to convert one mole of solid to liquid at its
melting point.

The energy that must be removed in order

to convert one mole of liquid to solid at its
freezing point.
Latent Heat of Phase Change #2

Molar Heat of Vaporization

The energy that must be absorbed in order
to convert one mole of liquid to gas at its
boiling point.

The energy that must be removed in order

to convert one mole of gas to liquid at its
condensation point.
 Latent Heat – Sample Problem
Problem: The molar heat of fusion of water is 6.009
kJ/mol. How much energy is needed to convert 60
grams of ice at 0C to liquid water at 0C?

60 g H 2O 1 mol H 2O 6.009 kJ
 20.00 kiloJoules
18.02 g H 2O 1 mol

Mass Molar Heat

of ice Mass of of
water fusion
 Heat of Reaction
The amount of heat released or absorbed
during a chemical reaction.
Endothermic:
Reactions in which energy is absorbed
as the reaction proceeds.

Exothermic:
Reactions in which energy is released
as the reaction proceeds.
 “loses” heat

 qAg  qH2O Calorimetry

  Cp  m  T    Cp  m  T 
  Cp  m   Tfinal  Tinitial     Cp  m   Tf  Ti  

Substitute values into equation.

   0.235 J go C  30 g  x - 100 o C     4.184 J go C  75 g  x - 25o C
Surroundings
Drop units and solve the algebra.
SYSTEM
705  7.05 x  313.8x  7845
8550  320.8x Tfinal = 26.7oC

x  26.6o C
H2 O Ag

m = 75 g m = 30 g
T = 25oC T = 100oC
 Calorimetry
 qAg  qH2O
  Cp  m  T    Cp  m  T 
  Cp  m   Tfinal  Tinitial     Cp  m   Tf  Ti  

Substitute values into equation.

   0.235 J go C   30 g  x - 100 o C    4.184 J go C  75 g  x - 25 o C 

Surroundings
Drop units and solve the algebra.
705  7.05 x  313.8x  7845 SYSTEM
320.8x  8550
x  26.7 o C

H2 O Ag

m = 75 g m = 30 g
T = 25oC T = 100oC
1 BTU (British Thermal Unit) – amount of heat needed to raise 1 pound of water 1oF.

1 calorie - amount of heat needed to raise 1 gram of water 1oC

1 Calorie = 1000 calories
“food” = “science”

Candy bar
300 Calories = 300,000 calories
English

Joules
Metric = _______ 1 calorie = 4.184 Joules
 140 DH = mol x DHvap
120 DH = mol x DHfus
100

Temperature (oC)
80
60 Heat = mass x Dt x Cp, gas
40
20 Heat = mass x Dt x Cp, liquid
0
-20
-40
-60

Cp(ice) = 2.077 J/g oC -80

-100
Heat = mass x Dt x Cp, solid

Time

It takes 2.077 Joules to raise 1 gram ice 1oC.

X Joules to raise 10 gram ice 1oC.
(10 g)(2.077 J/g oC) = 20.77 Joules

X Joules to raise 10 gram ice 10oC.

(10oC)(10 g)(2.077 J/g oC) = 207.7 Joules

q = Cp . m . DT
Heat = (specific heat) (mass) (change in temperature)
 140 DH = mol x DHvap
120 DH = mol x DHfus
100

Temperature (oC)
80
60 Heat = mass x Dt x Cp, gas
40
20 Heat = mass x Dt x Cp, liquid
0
-20
-40
-60
-80 Heat = mass x Dt x Cp, solid

q = Cp . m . DT -100

Time

Heat = (specific heat) (mass) (change in temperature)

Given Ti = -30oC q  Cp(ice)  m  T

Tf = -20oC
q  Cp(ice)  m   Tfinal  Tinitial 

 2.077 J 
q   10 g   - 20o
C  ( 30o
C)
 g C 
o

q = 207.7 Joules
240 g of water (initially at 20oC) are mixed with an unknown mass of iron (initially at 500 oC).
When thermal equilibrium is reached, the system has a temperature of 42 oC.
Find the mass of the iron.

T = 500oC
Fe mass = ? grams

T = 20oC
mass = 240 g - LOSE heat = GAIN heat

- [(Cp,Fe) (mass) (DT)] = (Cp,H O) (mass) (DT)

2

- [(0.4495 J/goC) (X g) (42oC - 500oC)] = (4.184 J/goC) (240 g) (42oC - 20oC)]

Drop Units: - [(0.4495) (X) (-458)] = (4.184) (240 g) (22)

205.9 X = 22091
X = 107.3 g Fe

Calorimetry Problems 2
question #5
A 97 g sample of gold at 785oC is dropped into 323 g of water, which has an initial
temperature of 15oC. If gold has a specific heat of 0.129 J/g oC, what is the final
temperature of the mixture? Assume that the gold experiences no change in state
of matter.

T = 785oC
Au mass = 97 g

T = 15oC
mass = 323 g
- LOSE heat = GAIN heat

- [(Cp,Au) (mass) (DT)] = (Cp,H O) (mass) (DT)

2

Drop Units: - [(0.129 J/goC) (97 g) (Tf - 785oC)] = (4.184 J/goC) (323 g) (Tf - 15oC)]
- [(12.5) (Tf - 785oC)] = (1.35 x 103) (Tf - 15oC)]
-12.5 Tf + 9.82 x 103 = 1.35 x 103 Tf - 2.02 x 104
3 x 104 = 1.36 x 103 Tf
Tf = 22.1oC

Calorimetry Problems 2
question #8
If 59 g of water at 13oC are mixed with 87 g of water at 72oC, find the final temperature
of the system.

T = 13oC T = 72oC
mass = 59 g mass = 87 g

- LOSE heat = GAIN heat

- [(Cp,H O) (mass) (DT)] = (Cp,H O) (mass) (DT)

2 2

Drop Units: - [(4.184 J/goC) (87 g) (Tf - 72oC)] = (4.184 J/goC) (59 g) (Tf - 13oC)
- [(364.0) (Tf - 72oC)] = (246.8) (Tf - 13oC)
-364 Tf + 26208 = 246.8 Tf - 3208
29416 = 610.8 Tf
Tf = 48.2oC

Calorimetry Problems 2
question #9
 A 38 g sample of ice at -11oC is placed into 214 g of water at 56oC.
Find the system's final temperature.
140 DH = mol x DHvap
120 DH = mol x DHfus
100

Temperature (oC)
80
60 Heat = mass x Dt x Cp, gas
40
T = -11oC 20
0
Heat = mass x Dt x Cp, liquid

ice mass = 38 g -20

-40
D -60
water cools -80 Heat = mass x Dt x Cp, solid

B -100

A warm
C water Time

melt ice
warm ice
T = 56oC
mass = 214 g
- LOSE heat = GAIN heat
D A B C
- [(Cp,H O(l)) (mass) (DT)] = (Cp,H O(s)) (mass) (DT) + (Cf) (mass) + (Cp,H O(l)) (mass) (DT)
2 2 2

- [(4.184 J/goC)(214 g)(Tf - 56oC)] = (2.077 J/goC)(38 g)(11oC) + (333 J/g)(38 g) + (4.184 J/goC)(38 g)(Tf - 0oC)
- [(895) (Tf - 56oC)] = 868 + 12654 + (159) (Tf)]
- 895 Tf + 50141 = 868 + 12654 + 159 Tf
- 895 Tf + 50141 = 13522 + 159 Tf
36619 = 1054 Tf
Tf = 34.7oC
Calorimetry Problems 2
question #10
 (1000 g = 1 kg)
238.4kg
25 g of 116oC steam are bubbled into 0.2384 g of water at 8 oC. Find the final temperature of the system.

- [qA + qB + qC] = qD
- [(Cp,H O) (mass) (DT)] + (-Cv,H O) (mass) + (Cp,H O) (mass) (DT) = [(Cp,H O) (mass) (DT)]
2 2 2 2

qD = (4.184 J/goC) (238.4 g) (Tf - 8oC)

qD = 997Tf - 7980

qA = [(Cp,H O) (mass) (DT)]

2 qB = (Cv,H O) (mass)
2
qC = [(Cp,H O) (mass) (DT)]
2

qA = [(1.87 J/goC) (25 g) (100o - 116oC)] qB = (-2256 J/g) (25 g) qC = [(4.184 J/goC) (25 g) (Tf - 100oC)]
qA = - 748 J qB = - 56400 J qC = 104.5Tf - 10460

- [qA + qB + qC] = qD
140
- [ - 748 + -56400 + 104.5Tf - 10460] = 997Tf - 7980 120 DH = mol x DHfus
DH = mol x DHvap

100
748 + 56400 - 104.5Tf + 10460 = 997Tf - 7980

Temperature (oC)
80
60 Heat = mass x Dt x Cp, gas
40
67598 - 104.5Tf = 997Tf - 7979 20
0
Heat = mass x Dt x Cp, liquid
A -20
75577 = 1102Tf -40
C -60
1102 1102 -80 Heat = mass x Dt x Cp, solid

B -100
Tf = 68.6oC
Time
D
Calorimetry Problems 2
question #11
 (1000 g = 1 kg)
238.4kg
25 g of 116oC steam are bubbled into 0.2384 g of water at 8 oC. Find the final temperature of the system.

- [qA + qB + qC] = qD
- [(Cp,H O) (mass) (DT) + (-Cv,H O) (mass) + (Cp,H O) (mass) (DT)] = (Cp,H O) (mass) (DT)
2 2 2 2

- [(Cp,H O) (mass) (DT) +

2 (Cv,H O) (mass) +
2
(Cp,H O) (mass) (DT)] = (4.184 J/goC) (238.4 g) (Tf - 8oC)
2

- [(1.87 J/goC) (25 g) (100o - 116oC) + (-2256 J/g) (25 g) + (4.184 J/goC) (25 g) (Tf - 100oC)] = 997Tf - 7980

-[ - 748 J + - 56400 J + 104.5Tf - 10460 ] = 997Tf - 7980

- [ - 748 + -56400 + 104.5Tf - 10460] = 997Tf - 7980

748 + 56400 - 104.5Tf + 10460 = 997Tf - 7980

67598 - 104.5Tf = 997Tf - 7979

140 DH = mol x DHvap
75577 = 1102Tf 120 DH = mol x DHfus
100
1102 1102

Temperature (oC)
80
60 Heat = mass x Dt x Cp, gas
Tf = 68.6 C o 40
20 Heat = mass x Dt x Cp, liquid
0
A -20
-40
C -60
Heat = mass x Dt x Cp, solid
-80
B -100

Time
D
Calorimetry Problems 2
question #11
A 322 g sample of lead (specific heat = 0.138 J/g oC) is placed into 264 g of water at 25oC.
If the system's final temperature is 46oC, what was the initial temperature of the lead?

T = ? oC
Pb mass = 322 g

Ti = 25oC Tf = 46oC
mass = 264 g Pb
- LOSE heat = GAIN heat

- [(Cp,Pb) (mass) (DT)] = (Cp,H O) (mass) (DT)

2

Drop Units: - [(0.138 J/goC) (322 g) (46oC - Ti)] = (4.184 J/goC) (264 g) (46oC- 25oC)]
- [(44.44) (46oC - Ti)] = (1104.6) (21oC)]
- 2044 + 44.44 Ti = 23197
44.44 Ti = 25241
Ti = 568oC

Calorimetry Problems 2
question #12
 A sample of ice at –12oC is placed into 68 g of water at 85oC. If the final temperature
of the system is 24oC, what was the mass of the ice?

T = -12oC
H2O mass = ? g

ice
Ti = 85oC Tf = 24oC
mass = 68 g

qA = [(Cp,H O) (mass) (DT)]

2
GAIN heat = - LOSE heat

qA = [(2.077 J/goC) (mass) (12oC)] 24.9 m [ qA + qB + qC ] = - [(Cp,H O) (mass) (DT)]

2

[ qA + qB + qC ] = - [(4.184 J/goC) (68 g) (-61oC)]

qB = (Cf,H O) (mass)
2

qB = (333 J/g) (mass) 333 m 458.2 m = - 17339

458.2 458.2
qC = [(Cp,H O) (mass) (DT)]
2

qC = [(4.184 J/goC) (mass) (24oC)] 100.3 m m = 37.8 g

qTotal = qA + qB + qC 458.2 m

Calorimetry Problems 2
question #13
 Endothermic Reaction
Energy + Reactants  Products

Activation
Energy

Energy Products

Reactants
+DH Endothermic

Reaction progress
Calorimetry Problems 1

Calorimetry 1

Calorimetry 1

Keys
Keys

http://www.unit5.org/chemistry/Matter.html
Calorimetry Problems 2

Calorimetry 2 
Specific Heat Values

Calorimetry 2 
Specific Heat Values

Keys
Keys

http://www.unit5.org/chemistry/Matter.html
Heat Energy Problems

Heat
  Energy Problems
Heat Problems (key)         
Heat Energy of Water Problems (Calorimetry)
Specific Heat Problems

Heat
  Energy Problems
Heat Problems (key)         
Heat Energy of Water Problems (Calorimetry)
Specific Heat Problems

Keys
Keys
aa bb cc
http://www.unit5.org/chemistry/Matter.html
 Enthalpy Diagram
H2(g) + ½ O2(g)

DH = +242 kJ -242 kJ -286 kJ DH = -286 kJ

Endothermic Exothermic Endothermic Exothermic
Energy

HH22O(g)
O(g)
- 44 kJ
Exothermic
+44 kJ
Endothermic

HH22O(l)
O(l)
H2(g) + 1/2O2(g)  H2O(g) + 242 kJ D H = -242 kJ
Kotz, Purcell, Chemistry & Chemical Reactivity 1991, page 211
 Hess’s Law
Calculate the enthalpy of formation of carbon dioxide from its elements.
C(g) + 2O(g)  CO2(g)

Use the following data:

2O(g)O2O
2O(g) 2(g)
(g) DHDH= =- 250
- 250kJkJ
C(g) C(s)
C(s) C(g) DHDH= =- 720 kJkJ
+720
C(s)
CO+ O (g)  CO (g)
2(g) 2 C(s) +2 O2(g)
DHDH= =- 390
+390kJkJ

C(g) + 2O(g)  CO2(g) DH = -1360 kJ

Smith, Smoot, Himes, pg 141

In football, as in Hess's law, only the initial and final conditions matter.
A team that gains 10 yards on a pass play but has a five-yard penalty,
has the same net gain as the team that gained only 5 yards.

10 yard pass

5 yard net gain

5 yard penalty

initial position final position

of ball of ball