Chapter 6:

Energy and
Chemical Change
 6.3 Measuring Heat
 6.4 Energy of Chemical Reactions
 6.5 Heat, Work, and the First Law of
Thermodynamics
 6.6 Heats of Reaction
 6.7 Thermochemical Equations
 6.8 Hess’s Law
 6.9 Standard Heats of Reaction

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 2

 Heat Capacity (C )
 Amount of heat (q) required to raise temperature
of object by 1 °C
Heat Exchanged = Heat Capacity × t
q = C × t
 Units for C = J/°C or J°C –1

 Extensive property
 Depends on two factors
1. Sample size or amount (mass)
 Doubling amount doubles heat capacity
2. Identity of substance
 Water vs. iron
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 3
 Learning Check: Heat Capacity
A cup of water is used in an experiment. Its heat
capacity is known to be 720 J/ ˚C. How much
heat will it absorb if the experimental
temperature changed from 19.2 ˚C to 23.5 ˚ C?

q = 3.1 × 103 J
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 4
 Your Turn!
What is the heat capacity of 300. g of an object
if it requires 2510. J to raise the temperature of
the object by 2.00˚ C?
A. 4.18 J/˚ C
B. 418 J/˚ C 1255 J/°C
C. 837 J/˚ C
D. 1.26 × 103 J/˚ C
E. 2.51 × 103 J/°C

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 5

 Specific Heat (s)
 Amount of Heat Energy needed to raise
temperature of 1 g substance by 1 °C
C=s×m or C
s 
 Intensive property m
 Ratio of two extensive properties
 Units
 J/(g °C) or J g1 °C1
 Unique to each substance
 Large specific heat means substance releases
large amount of heat as it cools
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 6
 Your Turn!
The specific heat of silver 0.235 J g–1 °C–1. What is
the heat capacity of a 100. g sample of silver?
A. 0.235 J/°C
B. 2.35 J/°C
C. 23.5 J/°C
D. 235 J/°C
E. 2.35 × 103 J/°C

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 7

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 8
 Using Specific Heat
Heat Exchanged = (Specific Heat  mass)  t
q = s  m  t
Units = J/(g °C)  g  °C = J
 Substances with high specific heats resist changes
in temperature when heat is applied
 Water has unusually high specific heat
 Important to body (~60% water)

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 9

 Your Turn!
The specific heat of copper metal is 0.385 J/(g ˚C).
How many J of heat are necessary to raise the
temperature of a 1.42 kg block of copper from
25.0 ˚C to 88.5 ˚C?
A. 547 J
B. 1.37 × 104 J
C. 3.47 × 104 J
D. 34.7 J
E. 4.74 × 104 J

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 10

 Direction of Heat Flow
 Heat is the energy transferred between two
objects
 Heat lost by one object has the same magnitude as
heat gained by other object
 Sign of q indicates direction of heat flow
 Heat is gained, q is positive (+)
 Heat is lost, q is negative (–)
q1 = –q2

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 11

 Ex. 1 Using Heat Capacity
A ball bearing at 260˚ C is dropped into a cup
containing 250. g of water. The water warms from
25.0 to 37.3 ˚C. What is the heat capacity of the ball
bearing in J/˚ C?
Heat capacity of the cup of water = 1046 J / ˚C
qlost by ball bearing = –qgained by water
1. Determine temperature change of water
t water
= (37.3 ˚ C – 25.0 ˚C) = 12.3 ˚C
2. Determine how much heat gained by water
qwater = Cwater  twater = 1046 J/˚C  12.3 ˚C
= 12.87 ×103 J
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 12
Ex. 1 Using Heat Capacity (cont)

3. Determine how much heat ball bearing lost

qball bearing = – qwater = –12.87 × 103 J
4. Determine T change of ball bearing
t ball bearing = (37.3 ˚C – 260 ˚C) = –222.7 ˚ C
5. Calculate C of ball bearing

= 57.8 J/˚ C
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 13
 Work
Work = –P × V
 P = opposing pressure against which piston
pushes
 V = change in volume of gas during expansion
 V = Vfinal – Vinitial
 For Expansion
 Since Vfinal > Vinitial
 V must be positive
 So expansion work is negative
 Work done by system
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 14
 Your Turn!
Calculate the work associated with the expansion
of a gas from 152.0 L to 189.0 L at a constant
pressure of 17.0 atm.
A. 629 L atm Work = –P × V
B. –629 L atm
V = 189.0 L – 152.0 L
C. –315 L atm
D. 171 L atm w = –17.0 atm × 37.0 L
E. 315 L atm

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 15

First Law of Thermodynamics
the change in internal energy (E)

 E = q + w
q is (+) Heat absorbed by system (IN)
q is (–) Heat released by system (OUT)
w is (+) Work done on system (IN)
w is (–) Work done by system (OUT)

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 16

 Your Turn!
A gas releases 3.0 J of heat and then performs
12.2 J of work. What is the change in internal
energy of the gas?
A. –15.2 J E= q+w
B. 15.2 J E = – 3.0 J + (–12.2 J)
C. –9.2 J
D. 9.2 J
E. 3.0 J

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 17

Bomb Calorimeter (Constant V)
 Apparatus for
measuring E in
reactions at constant
volume
 Vessel in center with
rigid walls
 Heavily insulated vat
 Water bath
 No heat escapes
 E = qv

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 18

 Ex. 4 Calorimeter Problem
When 1.000 g of olive oil is completely burned in pure
oxygen in a bomb calorimeter, the temperature of the
water bath increases from 22.000 ˚C to 26.049 ˚C.
How many KCal are in olive oil, per gram? The heat
capacity of the calorimeter is 9.032 kJ/˚C.
t = 26.049 ˚ C – 22.000 ˚C = 4.049 ˚C
qabsorbed by calorimeter = Ct = 9.032 kJ/°C × 4.049 ˚C
= 36.57 kJ
qreleased by oil = – qcalorimeter = – 36.57 kJ

–8.740 KCal/g oil

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 19
 Your Turn!
A bomb calorimeter has a heat capacity of 2.47 kJ/K.
When a 3.74×10–3 mol sample of ethylene was burned
in this calorimeter, the temperature increased by 2.14
K. Calculate the energy of combustion for one mole of
ethylene.
A. –5.29 kJ/mol qcal = Ct
B. 5.29 kJ/mol = 2.47 kJ/K × 2.14 K = 5.286 kJ
C. –148 kJ/mol
qethylene = – qcal = – 5.286 kJ
D. –1410 kJ/mol
E. 1410 kJ/mol

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 20

 Enthalpy (H)
 Heat of reaction at constant Pressure (qP)
H = qP

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 21

 Enthalpy Change (H)
H is a state function
 H = Hfinal – Hinitial
 H = Hproducts – Hreactants
 Significance of sign of H
Endothermic reaction
 System absorbs energy from surroundings
 H positive
Exothermic reaction
 System loses energy to surroundings
 H negative
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 22
 Coffee Cup Calorimeter
 Simple
 Measures qP
 Open to atmosphere
 Constant P
 Let heat be exchanged between
reaction and water, and
measure change in temperature
 Very little heat lost
 Calculate heat of reaction
 qP = Ct

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 23

 Ex. 5 Coffee Cup Calorimetry
NaOH and HCl undergo rapid and exothermic reaction
when you mix 50.0 mL of 1.00 M HCl and 50.0 mL of
1.00 M NaOH. The initial t = 25.5 °C and final t =
32.2 °C. What is H in kJ/mole of HCl? Assume for
these solutions s = 4.184 J g–1°C–1. Density: 1.00 M
HCl = 1.02 g mL–1; 1.00 M NaOH = 1.04 g mL–1.
NaOH(aq) + HCl(aq)  NaCl(aq) + H2O(aq)
qabsorbed by solution = mass  s  t
massHCl = 50.0 mL  1.02 g/mL = 51.0 g
massNaOH = 50.0 mL  1.04 g/mL = 52.0 g
massfinal solution = 51.0 g + 52.0 g = 103.0 g
t = (32.2 – 25.5) °C Chemistry:
Jespersen/Brady/Hyslop
= 6.7The°C
Molecular Nature of Matter, 6E 24
 Ex. 5 Coffee Cup Calorimetry
qcal = 103.0 g  4.184 J g–1 °C–1  6.7 °C = 2890 J
Rounds to qcal = 2.9  103 J = 2.9 kJ
qrxn = –qcalorimeter = –2.9 kJ
1 mol HCl
0.0500 L HCl soln 
1 L HCl soln
= 0.0500 mol HCl
Heat evolved per mol HCl =

= -58 kJ/mol

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 25

 Ex. : Coffee Cup Calorimetry
When 50.0 mL of 0.987 M H2SO4 is added to 25.0 mL of
2.00 M NaOH at 25.0 °C in a calorimeter, the
temperature of the aqueous solution increases to 33.9
°C. Calculate H in kJ/mole of NaOH.
Assume: specific heat of the solution is 4.184 J/g°C,
density is 1.00 g/mL, and the calorimeter absorbs a
negligible amount of heat.
Write balanced equation
2NaOH(aq) + H2SO4(aq)  Na2SO4(aq) + 2H2O(aq)
Determine heat absorbed by calorimeter
masssoln = (25.0 mL + 50.0 mL) × 1.00 g/mL = 75.0 g
qsoln = 75.0 g × (33.9 – 25.0)°C × 4.184 J/g°C = 2.8×103 J
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 26
 1 L NaOH 2 mol NaOH
25.0 mL NaOH  
1000 mL NaOH 1 L NaOH

= 0.0500 mol NaOH present

 2.8  10 3 J 1 kJ
H   = –56 kJ/mol
0.0500 mol NaOH 1000 J

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

 Thermochemical Equation
 Write H immediately after equation
N2(g) + 3H2(g)  2NH3(g) H= –92.38 kJ
 Assumes coefficients is the number of moles
 92.38 kJ released when 2 moles of NH3 formed
 If 10 mole of NH3 formed
5N2(g) + 15H2(g)  10NH3(g) H= –461.9 kJ
 H° = (5 × –92.38 kJ) = – 461.9 kJ
 Can have fractional coefficients
 Fraction of mole, NOT fraction of molecule
½N2(g) + 3/2H2(g)  NH3(g) H°rxn = –46.19 kJ
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 28
 Learning Check:
Given the equation below, how many kJ are required
for 44 g CO2 (MM = 44.01 g/mol)?
6CO2(g) + 6H2O → C6H12O6(s) + 6O2(g) ΔH˚reaction = 2816 kJ

1 mol CO 2 2816 kJ
44 g CO 2    470 kJ
44.01 g CO 2 6 mol CO 2
If 100. kJ are provided, what mass of CO 2 can be
converted to glucose?
6 mol CO2 44.0 g CO2
100 kJ    9.38 g
2816 kJ 1 mol CO2

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 29

 Your Turn!
Based on the reaction
CH4(g) + 4Cl2(g)  CCl4(g) + 4HCl(g)
H˚reaction = – 434 kJ/mol CH4
What energy change occurs when 1.2 moles of
methane reacts?
A. – 3.6 × 102 kJ H = –434 kJ/mol × 1.2 mol

B. +5.2 × 102 kJ H = –520.8 kJ = -5.2 × 102 kJ

C. – 4.3 × 102 kJ
D. +3.6 × 102 kJ
E. – 5.2 × 102 kJ
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 30
Hess’s Law of Heat Summation
 For any reaction that can be written into steps, value
of H °rxn for reactions = sum of H °rxn values of
each individual step

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 31

 Rules for Manipulating
Thermochemical Equations
1. When equation is reversed, sign of H°rxn must
also be reversed.
2. If all coefficients of equation are multiplied or
divided by same factor, value of H°rxn must
likewise be multiplied or divided by that factor
3. Formulas canceled from both sides of equation
must be for substance in same physical states

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 32

 Ex. 9 Calculate H°rxn for
C (s, graphite)  C (s, diamond)
Given C (s, gr) + O2(g)  CO2(g) H°rxn = –394 kJ
–1[ C (s, dia) + O (g)  CO (g) H°rxn = –396 kJ ]
2 2

 To get desired equation, must reverse second

equation and add resulting equations
C(s, gr) + O2(g)  CO2(g) H°rxn = –394 kJ
CO2(g)  C(s, dia) + O2(g) H°rxn = –(–396 kJ)
C(s, gr) + O2(g) + CO2(g)  C(s, dia) + O2(g) + CO2(g)

H° = –394 kJ + 396 kJ = + 2 kJ

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 33
 Learning Check: Ex. 10
Calculate H °rxn for
2 C (s, gr) + H2(g)  C2H2(g)
Given the following:
a. C2H2(g) + 5/2O2(g)  2CO2(g) + H2O(l )
H °rxn = –1299.6
kJ
b. C(s, gr) + O2(g)  CO2(g) H °rxn = –393.5 kJ
c. H2(g) + ½O2(g)  H2O(l ) H °rxn = –285.8 kJ

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 34

 Ex.10 Calculate for
2C(s, gr) + H2(g)  C2H2(g)
2CO2(g) + H2O(l )  C2H2(g) + 5/2O2(g)
H°rxn = – (–1299.6 kJ) = +1299.6 kJ
2C(s, gr) + 2O2(g)  2CO2(g)
H°rxn =(2 –393.5 kJ) = –787.0 kJ
H2(g) + ½O2(g)  H2O(l ) H°rxn = –285.8 kJ
2CO2(g) + H2O(l ) + 2C(s, gr) + 2O2(g) + H2(g) + ½O2(g)
 C2H2(g) + 5/2O2(g) + 2CO2(g) + H2O(l )
2C(s, gr) + H2(g)  C2H2(g) H°rxn = +226.8 kJ

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 35

 Your Turn!
Given the following data:
C2H2(g) + O2(g)  2CO2(g) + H2O(l ) H rxn = –1300. kJ
C(s) + O2(g)  CO2(g) Hrxn = –394 kJ
H2(g) + O2(g)  H2O(l ) Hrxn = –286 kJ
Calculate for the reaction
2C(s) + H2(g)  C2H2(g)
A. 226 kJ
B. –1980 kJ
Hrxn = +1300. kJ + 2(–394 kJ) + (–286 kJ)
C. –620 kJ
D. –226 kJ
E. 620 kJ
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 36
Standard Enthalpy of Formation, Hf°
 Amount of heat absorbed or evolved when one
mole of substance is formed at 1 atm (1 bar) and
25 °C (298 K) from elements in their standard
states

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 37

 Standard State
 Most stable form and physical state of
element at 1 atm (1 bar) and 25 °C (298 K)
Element Standard Note: All Hf° of
state
elements in their
O O2(g) standard states = 0
C C (s, gr)
Forming element from
H H2(g)
itself.
Al Al(s)
Ne Ne(g)
 See Appendix C in back of textbook and Table 7.2

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 38

Uses of Standard Enthalpy (Heat)
of Formation, Hf°
1. From definition of Hf°, can write balanced
equations directly
Hf° of Fe2O3(s)
2Fe(s) + 3/2O2(g)  Fe2O3(s) Hf° = –822.2 kJ/mol

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 39

 Your Turn!
What is the reaction that corresponds to the standard
enthalpy of formation of NaHCO3(s ), Hf ° = – 947.7
kJ/mol?

A. Na(s) + ½H2(g) + 3/2O2(g) + C(s, gr)  NaHCO3(s)

B. Na+(g) + H+(g) + 3O2–(g) + C4+(g)  NaHCO3(s)
C. Na+(aq) + H+(aq) + 3O2–(aq) + C4+(aq)  NaHCO3(s)
D. NaHCO3(s)  Na(s) + ½H2(g) + 3/2O2(g) + C(s, gr)
E. Na+(aq) + HCO3–(aq)  NaHCO3(s)

Answer: A
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 40
 Ex. 11 Calculate H°rxn Using Hf°
Calculate H°rxn using Hf° data for the reaction
SO3(g)  SO2(g) + ½O2(g)

H°rxn has units of kJ

H°f has units of kJ/mol


H rxn  H f (SO 2 ( g ))  1
2 H 
f (O 2 ( g ) )  H 
f (SO 3 ( g ))

H°rxn = 99 kJ
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 41
 Learning Check
Calculate H for this reaction using Hf° data.
2Fe(s) + 6H2O(l)  2Fe(OH)3(s) + 3H2(g)
Hf° 0 –285.8 –696.5 0

H°rxn = 2×Hf°(Fe(OH)3, s) + 3×Hf°(H2, g)

– 2× Hf°(Fe, s) – 6×Hf°(H2O, l )
H°rxn = 2 mol× (– 696.5 kJ/mol) + 3×0 – 2×0
– 6 mol× (–285.8 kJ/mol)
H°rxn = –1393 kJ + 1714.8 kJ
H°rxn = 321.8 kJ

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 42