Energy and Chemical Change: Chemistry: The Molecular Nature of Matter, 7E

Chapter 7
Energy and
Chemical Change
Chemistry: The Molecular Nature

of Matter, 7E
Jespersen/Hyslop
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved.
Thermochemistry
 Study of energies given off by or absorbed by
reactions
Thermodynamics
 Study of heat transfer or heat flow
Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 2
Units of Energy
A calorie (cal)
 Energy needed to raise the temperature of
1 g H2O by 1 °C
 1 cal = 4.184 J
 1 kcal = 1000 cal
 1 kcal = 4.184 kJ
1. System, Surroundings and Boundary
System
 What we are interested in studying
 Reaction in beaker
Surroundings
 Everything else
 Room in which reaction is run
Boundary
 Separation between system and surroundings
 Visible Example: Walls of beaker
 Invisible Example: Line separating warm and cold
fronts
Systems
Open System
 Open to atmosphere
 Gain or lose mass and energy
across boundary
 Most reactions done in open Open system
systems
Closed System
 Not open to atmosphere
 Energy can cross boundary,
but mass cannot
Closed system
Isolated System
 No energy or matter can cross
boundary
 Energy and mass are constant
Example: Thermos bottle
Isolated system
2. Heat (q), Heat Capacity (C) and Specific Heat (S)
Heat (q)
 Heat (q) gained or lost by an object
 Directly proportional to temperature change (t) it
undergoes
 Adding heat, increases temperature
 Removing heat, decreases temperature
 Measure changes in temperature to quantify
amount of heat transferred
q = C × t
 C = heat capacity
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
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
Heat Exchanged = (Specific Heat  mass)  t
q = s  m  t
Units = J/(g °C)  g  °C = J
EX: Calculate the specific heat of water if the heat
capacity of 100. g of water is 418 J/°C.

418 J/ C
s   4.18 J/g °C
100. g
 What is the specific heat of water if heat
capacity of 1.00 g of water is 4.18 J/°C?

4.18 J/ C
s   4.18 J/g °C
1.00 g
 Thus, heat capacity is independent of amount of
substance
EX: 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
EX: 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
EX: A copper mug has a heat capacity of 77.5 J/˚C.
After adding hot water to the mug, the temperature
of the mug changed from 77.0 ˚F to 185 ˚F. How
much heat did the mug absorb from the water?
A. 4.65 × 103 J q  C  t  77.5 J/ oC  t
B. 1.29 J Note units: temps. must be in oC
C. 8.37 × 103 J ti = 25.0 oC, tf = 85.0 oC,
D. 5.97 × 10 J
3 So Dt = 85.0 o
C – 25.0 o
C = 60.0 o
C
E. 1.43 × 104 J 77.5 J o
q o  60.0 C
C
= 4.65 × 103 J
EX: 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 J
C  23.5 
E. 2.35 × 103 J/°C C
EX: Calculate the specific heat of a metal if it
takes 235 J to raise the temperature of a 32.91 g
sample by 2.53 °C.
EX: 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
4
q  3.47  10 J
3. Bomb Calorimeter (Constant
V)  Apparatus for measuring
E in reactions at
constant volume
 Vessel in center with
rigid walls
 No change in volume, so
DV = 0 so PDV = 0
 Heavily insulated vat
 Water bath
 No heat escapes
 E = q - PDV
 E = q + 0 = qv
 subscript ‘v’ emphasizes
constant volume
EX: 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. q = C t cal
A. –5.29 kJ/mol
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
E ethylene  1410 kJ/mol
4. 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
5. Exothermic and Endothermic Reactions
Exothermic Reaction
 Reaction where products have less chemical
energy than reactants
 Reaction releases heat energy to surroundings
 Heat leaves the system; q is negative ( – )
 Reaction gets warmer, temperature increases
Example:
CH4(g) + 2O2(g)  CO2(g) + 2H2O(g) + heat
Endothermic Reaction
 Reaction where products have more energy than
reactants
 Reaction absorbs heat from surroundings
 Heat added to system; q is positive (+)
Example: Photosynthesis
6CO2(g) + 6H2O(g) + solar energy 
C6H12O6(s) + 6O2(g)
6. First Law of Thermodynamics
 In an isolated system, the change in internal
energy (E) is constant:
E = E f – Ei = 0
 Can’t measure internal energy of anything
 Can measure changes in energy
E is state function
E = heat + work
E = q + w
E = heat input + work input
Work Convention
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
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 = 37.0 L
C. –315 L atm
D. 171 L atm w = –17.0 atm × 37.0 L
E. 315 L atm
Your Turn!
A chemical reaction took place in a 6 liter
cylindrical enclosure fitted with a piston. Over the
course of the reaction, the system underwent a
volume change from 0.400 liters to 3.20 liters.
Which statement below is always true?
A. Work was performed on the system.
B. Work was performed by the system.
C. The internal energy of the system increased.
D. The internal energy of the system decreased.
E. The internal energy of the system remained
unchanged.
 Energy of system may be transferred as heat or
work, but not lost or gained
 If we monitor heat transfers (q) of all materials
involved and all work processes, can predict
that their sum will be zero
 Some energy transfers will be positive, gain in
energy
 Some energy transfers will be negative, a loss in
energy
 By monitoring surroundings, we can predict
what is happening to system
 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)
Endothermic reaction
 E = +
Exothermic reaction
 E = –
EX: A reaction contracts by 1.534 L under a
constant pressure of 2.134 atm while releasing
200.7 J of heat to the surrounding. What is the
change in internal energy of the system? 1.000
Latm = 101.3 J E = q + w = -200.7 J + w
A. 131.0 J Work = –P ×V
B. 532.4 J = -2.134 atm × 1.534 L = 3.274 Latm
C. -131.0 J 101.3 J
 3.274 Latm   331.7 J
D. -532.4 J 1.000 Latm
E. 331.6 J E = q + w = -200.7 J + 331.7
= 131.0 J
Enthalpy Changes in Chemical
Reactions
 Focus on systems
 Endothermic
 Reactants + heat  products
 Exothermic
 Reactants  products + heat
 Want convenient way to use enthalpies to
calculate reaction enthalpies
 Need way to tabulate enthalpies of reactions
H in Chemical Reactions
Standard Conditions for H 's
 25 °C and 1 atm and 1 mole
Standard Heat of Reaction (H ° )
 Enthalpy change for reaction at 1 atm and 25 °C
Example:
N2(g) + 3H2(g)  2 NH3(g)
1.000 mol 3.000 mol 2.000 mol
 When N2 and H2 react to form NH3 at 25 °C and 1
atm 92.38 kJ released
 H = –92.38 kJ
Thermochemical Equation
 Write H immediately after equation
N2(g) + 3H2(g)  2NH3(g) H = –92.38 kJ
 Must give physical states of products and
reactants
 H different for different states
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l ) H ° rxn = –890.5 kJ
CH4(g) + 2O2(g)  CO2(g) + 2H2O(g) H ° rxn = –802.3 kJ
 Difference is equal to the energy to vaporize
water
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
State Matters!
C3H8(g) + 5O2(g) → 3 CO2(g) + 4 H2O(g)
ΔH °rxn= –2043 kJ
C3H8(g) + 5O2(g) → 3 CO2(g) + 4 H2O(l )
ΔH °rxn = –2219 kJ
Note: there is difference in energy because
states do not match
If H2O(l ) → H2O(g) ΔH °vap = 44 kJ/mol
4H2O(l ) → 4H2O(g) ΔH °vap = 176 kJ/mol
7. The Standard State
 A standard state specifies all the necessary
parameters to describe a system. Generally this
includes the pressure, temperature, and amount
and state of the substances involved
 Standard state in thermochemistry
 Pressure = 1 atmosphere
 Temperature = 25 °C = 298 K
 Amount of substance = 1 mol (for formation
reactions and phase transitions)
 Amount of substance = moles in an equation
(balanced with the smallest whole number
coefficients)
8. Hess’s Law
Hess’s Law of Heat Summation
 Going from reactants to products
 Enthalpy change is same whether reaction takes
place in one step or many
 Calculation of H °rxn for reaction that can’t be
measured directly
 Thermochemical equations for individual steps
of reaction sequence may be combined to obtain
thermochemical equation of overall reaction
EX: Calculate Horxn 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

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
EX: Calculate Horxn 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
EX: 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
9. Tabulating H°values
 Need to Tabulate H° values
 Major problem is vast number of reactions
 Define standard reaction and tabulate these
 Use Hess’s Law to calculate H° for any other
reaction
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
 Standard heat of formation
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)
H H2(g) Forming element from
itself.
Al Al(s)
Ne Ne(g)
Uses of Standard Enthalpy (Heat)
of Formation, Hf°
1. From definition of Hf , can write balanced
equations directly
Hf° of C2H5OH(l )
2C(s, gr) + 3H2(g) + ½O2(g)  C2H5OH(l )
Hf° = –277.03 kJ/mol
Hf° of Fe2O3(s)
2Fe(s) + 3/2O2(g)  Fe2O3(s) Hf° = –822.2 kJ/mol
EX: Which reaction 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)
Using Hf°
2. Way to apply Hess’s Law without needing to manipulate
thermochemical equations
Sum of all H°f Sum of all H°f
H°reaction = of all of the – of all of the
products reactants
Consider the reaction:
aA + bB  cC + dD
H°reaction = c × H°f(C) + d × H°f(D)
– {a×H°f(A) + b×H°f(B)}
 H°rxn has units of kJ because
 Coefficients  heats of formation have units of mol  kJ/mol
H°rxn has units of kJ H°f has units of kJ/mol

Ex. 11: Calculate Horxn Using Hf°
Calculate H°rxn using Hf° data for the reaction
SO3(g)  SO2(g) + ½O2(g)
1. Multiply each Hf° (in kJ/mol) by the number of moles in the
equation
2. Add the Hf° (in kJ/mol) multiplied by the number of moles in the
equation of each product
3. Subtract the Hf° (in kJ/mol) multiplied by the number of moles in
the equation of each reactant
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
Learning Check
Calculate H°rxn using Hf° for the reaction
4NH3(g) + 7O2(g)  4NO2(g) + 6H2O(l )
H°rxn = [136 – 1715.4 + 184] kJ

H°rxn = –1395 kJ

Energy and Chemical Change: Chemistry: The Molecular Nature of Matter, 7E

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Energy and Chemical Change: Chemistry: The Molecular Nature of Matter, 7E

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Chapter 7

Chemistry: The Molecular Nature

C. –148 kJ/mol qethylene = – qcal = – 5.286 kJ

q is (+) Heat absorbed by system (IN)

 To get desired equation, must reverse second

H° = –394 kJ + 396 kJ = + 2 kJ

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

H°rxn has units of kJ H°f has units of kJ/mol

H°rxn has units of kJ

H°rxn = [136 – 1715.4 + 184] kJ

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