Ch7 Energy and Chemical Change PDF

Chapter
Ch t 7 7:
Energy and
Chemical Change
Chemistry: The Molecular Nature

of Matter,, 6E
J
Jespersen/Brady/Hyslop
/B d /H l
Thermochemistry
 Study of energies given off by or absorbed by
reactions.
Thermodynamics
 Study
St d off energy ttransfer
f (fl
(flow))
Energy (E)
 Ability to do work or to transfer heat.
Kinetic Energy (KE)
 Energy of motion
 KE = ½mv2
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 2

Potential Energy (PE)
 Stored energy
 Exists in natural attractions
and repulsions
 Gravity
 Positive and negative charges
 Springs
Chemical Energy
 PE possessed by chemicals
 Stored in chemical bonds
 Breaking bonds requires energy
 Forming bonds releases energy
Your Turn!
Which of the following is not a form of kinetic
energy?
A.A pencil rolls across a desk

B.A pencil is sharpened
C.A pencil is heated
D.A pencil rests on a desk
E A pencil falls to the floor
E.A

Factors Affecting Potential Energy
Increase Potential Energy
 Pull apart objects that attract
eachh other
th
 Book/gravity
 N and S poles of magnets
 Push together objects that repel
each other
 Spring compressed
 N poles on two magnets
 2 like charges
Factors Affecting Potential Energy
Decrease Potential Energy
 Objects that attract each other come together
 Book falls
 N and S poles of 2 magnets
 Objects that repel each
other move apart
 Spring released
 N poles on 2 magnets
 2 like
lik charges
h

Your Turn!
Which of the following represents a decrease in
the potential energy of the system?
A.A book is raised 6 feet above the floor.

B.A ball rolls downhill.
C.Two electrons come close together.
D.A spring is stretched completely.
E Two atomic nuclei approach each other.
E.Two other

Law of Conservation of Energy
 Energy can neither be created nor destroyed
 Can onlyy be
converted from
one form to
another
 Total Energy
of universe
is constant
Total = Potential + Kinetic

Energy Energy Energy
Temperature vs. Heat
Temperature
 Proportional to average kinetic energy of object’s
particles
 Higher average kinetic energy means
 Higher temperature
 Faster moving molecules
Heat
 Energy transferred between objects
 Caused by temperature difference
 Always passes spontaneously from warmer objects
j
to colder objects
 Transfers until both are the same temperature
Heat Transfer hot cold
 Hot and
d cold
ld objects
b placed
l d in
contact
 Molecules in hot object moving
faster
 KE transfers
f ffrom hotter to
colder object
 ↓ average KE of hotter object
 ↑ average KE of colder object
 Over time
 Average
g KEs of both objects
j becomes the same
 Temperature of both becomes the same
Units of Energy
JJoule
l (J)
 KE possessed by 2 kg object moving at speed
of 1 m/s.
m/s
2 2
1  1m  1 kg  m
1J  2kg   1J 
2  1s  s2
 If calculated value is greater than 1000 J, use

kJ
 1 kJ = 1000 J

Units of Energy
calorie (cal)
 Energy needed to raise T of 1 g H2O by 1 °C
C
 1 cal = 4.184 J (exactly)
 1 kcal = 1000 cal
 1 kcal = 4.184 kJ
1 nutritional
t iti l Calorie
C l i (Cal)
(C l)
 (note capital C)
 1 Cal = 1000 cal = 1 kcal
 1 kcal = 4.184 kJ

Your Turn!
Which is a unit of energy?
A.pascal
B.newton
C.joule
D watt
D.watt
E.ampere

Heat
 Pour hot
h coffee
ff into cold
ld cup
 Heat flows from hot coffee to cold cup
 Faster coffee molecules bump into wall of cup
 Transfer kinetic energy
 Eventually reach same temperature
Th
Thermal
l Equilibrium
E ilib i
 When both cup and coffee reach same
average Kinetic
Ki i Energy
E andd same temperature
 Energy transferred through heat comes from
object’s internal energy
Internal Energy (E)
 Sum of energies of all particles in system
E = Total energy of system
E = Potential + Kinetic = PE + KE
Change in Internal Energy
E = Efinal – Einitial
  means change
h
 final – initial
 What we can actually measure
 Want to know change in E associated with given
process
Molecular Kinetic Energy (MKE)
 Energy associated d with
h molecular
l l motion
 All particles within object are in constant motion
 Molecules moving through space/solution
 Atoms jjiggle
gg and vibrate within molecules
 Electrons move around atoms
 Each particle has certain value of MKE at any given
time
 Particles continually exchanging energy during
collisions
 In isolated sample, total kinetic energy of all
molecules is constant
E, Change in Internal Energy
 For reaction: reactants  products
d
 E = Eproducts – Ereactants
 Can use to do something useful
 Work
 Heat
H t
 If system absorbs energy during reaction
 Energy
E coming
i into
i t systemt is
i positive
iti (+)
 Final energy > initial energy
Photos nthesis or
Ex Photosynthesis
Ex. o charging
cha ging battery
 As system absorbs energy
 Increase potential energy
 Available for later use
Kinetic Molecular Theory
 Kinetic Molecular Theory tells us
Temperature
 Related to average kinetic energy of particles in
object
Internal energy
 Related to average
g total molecular kinetic
energy
 Includes molecular p
potential energy
gy
Average kinetic energy
 Implies distribution of kinetic energies among
molecules in object
Temperature and Average Kinetic
Energy
Large collection of molecules (gas)
 Wide distribution of kinetic energy (KE)
 Small number with KE = 0
 Collisions momentarily stopped molecule’s
motion
 Very small number with very high KE
 Unbalanced collisions give high velocity
 Most molecules intermediate KEs
 Result = distribution of energies
Distribution of Kinetic Energy
1 = lower T
2 = higher T
At higher T, distribution shifts to higher KE
Kinetic Energy Distribution
Temperature
 Average KE of all atoms and molecules in object
 Average speed of particles
 Kelvin Temperature
p of sample
p
 T(K) Avg MKE = ½ mvavg2
 At higher temperature
 Most molecules moving at higher average speed
 Cold
C ld object
bj t = Small
S ll average MKE
 Hot object = Large average MKE
Note: At 0 K KE = 0 so v=0
Kinetic Theory: Liquids and Solids
 Atoms and molecules in liquids and solids also
constantly moving
 Particles of solids jiggle and vibrate in place
 Distributions of KEs of particles in gas, liquid
and solid same at same T.
 At same T gas, liquid, and solid have
 Same average KE
 But
B t very different
diff t PE

Your Turn!
Which statement about kinetic energy (KE) is true?
A.Atoms and molecules in gases, liquids and solids
possess KE since they are in constant motion.
B.At the same temperature, gases, liquids and solids
all have different KE distributions.
C.Molecules in gases are in constant motion, while
molecules in liquids and solids are not.
D.Molecules in gases and liquids are in constant
motion, while molecules in solids are not.
E.As the temperature increases, molecules move more
slowly.
E, Change in Internal Energy
 E = Eproducts – Ereactants
 Energy
gy change
g can appear
pp entirelyy as heat
 Can measure heat
Can’tt measure Eproduct or Ereactant
 Can
 Fortunately, we are more interested in E
 Energy off system d
depends
d only
l on its
i current
condition
 DOES NOT depend
d d on:
 How system got it
 What E for system might be sometime in future
State of Object or System
 Complete
l list
l off properties that
h specify
f object’s
b ’
current condition
For Chemistry
 Defined byy p
physical
y properties
p p
 Chemical composition
 Substances
 Number of moles
 Pressure
 Temperature
 Volume

State Functions
 Any property that h only
l depends
d d on object’s
b ’
current state or condition
 Independence from method, path or mechanism
by which change occurs is important feature of
allll state functions
f i
 Some State functions:
 Internal energy  E = Ef – Ei
 Pressure P = Pf – Pi
 Temperature t = tf – ti
 Volume
l  V = Vf – Vi
State of an object
 If T = 25°C
25°C, tells us all we need to know
 Don’t need to know how system got to that T,
just that this is where it currently is
 If T  to 35°C, then change in T is simply:
 t = tfinal – tinitial
 Don’t need to know how this occurred, just need to
know initial and final values
 What does t tell us?
 Change in average MKE of particles in object
 Change in object’s total KE
 Heat energy
Defining the System
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 Ex. Walls of beaker
 Invisible Ex. Line separating warm and cold fronts
Three Types of Systems
Open System
 Open
p to atmosphere
p
 Gain or lose mass and energy
across boundaryy Open system
 Most reactions done in open
systems
y
Closed System
 Not open to atmosphere
 Energy can cross boundary,
but mass cannot
Closed system
Three Types of Systems
Isolated System
 No energy
gy or matter can cross
boundary
 Energy
gy and mass are constant
Ex. Thermos bottle
Adiabatic Process
 Process that occurs in isolated
system
y Isolated system
 Process where neither energy nor

matter crosses the
system/surrounding boundary
Your Turn!
A closed system can __________
A.include the surroundings.

B absorb energy and mass.
B.absorb mass
C.not change its temperature.
D.not absorb or lose energy and mass.
E.absorb or lose energy,
gy, but not mass.

Heat (q)
 Can’t measure heat directly
 Heat (q) gained
g or lost byy an object
j
 Directly proportional to temperature change (t) it
g
undergoes
 Adding heat, increases temperature
 Removing heat,
heat decreases temperature
 Measure changes in temperature to quantify
amountt off h
heatt ttransferred
f d
q = C × t
 C = heat capacity
Heat Capacity (C)
 Amount of heat (q) required to raise
temperature of object by 1 °C
H t Exchanged
Heat E h d=H Heatt C it × t
Capacity
q = C × t
 Units = J/°C or J°C –1
 Extensive property
p p y
 Depends on two factors
1 Sample size or amount (mass)
1.Sample
 Doubling amount doubles heat capacity
2 Identity of substance
2.Identity
 Water vs. iron
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  C  t
 23.5  19.2C 
J
q  720
C
 4.3C 
J
q  720
20
C
q = 3.1 × 103 J
Learning Check: Heat Capacity
 Iff it requires 4.184 J to raise the
h temperature off
1.00 g of water by 1.00 °C, calculate the heat
capacity it off 1
1.00
00 g off water.
t
q
C 
t
4.184 J
C 1.00 g  
 4.18 J/°C
1.00 C

Your Turn!
What
h is the
h heat
h capacity off 300 g off water iff it
requires 2510 J to raise the temperature of the
water
t bby 22.00
00 °C?
A.4.18 J/°C 2510 J
C 300 g  
B.418 J/°C 2.00  C
C 837 J/°C
C.837 J/ C
D.1.26 × 103 J/°C
E.2.51 × 103 J/°C

Specific Heat (s)
 Amount off Heat Energy needed
d d to raise T off 1 g
substance by 1 °C
C
C=s×m or s 
m
 Intensive property
 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
Learning Check
 Calculate the specific heat of water if it the heat
capacity of 100 g of water is 418 J/°C.
C 418 J/ C 
s  s   4.18 J/(g°C)
m 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
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 C  sm
B.2.35 J/
J/°C
C
J
C.23.5 J/°C C  0.235  100. g
g  C
D 235 J/°C
D.235
E.2.35 × 103 J/°C

Using Specific Heat
H
Heat E
Exchanged
h d = (S
(Specific
ifi HHeat  mass))  t
q = s  m  t
Units = J/(g  °C)  g  °C = J
 Substances with high
g specific
p heats resist T
changes
 Makes it difficult to change
g temperature
p widelyy
 Water has unusually high specific heat
 Important to body (~60%
( 60% water)
 Used to cushion temperature changes
 Why coastal temperatures are different from inland
temperatures
Learning Check: Specific Heat
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.
q  m  s  t
q 235J
s  
m  t 32.91g  2.53 C 
J
s  2.82 
g C
Your Turn!
The specific heat of copper metal is 0 0.385
385 J/(g
J/(g∙°C).
°C)
How many J of heat are necessary to raise the
temperature of a 11.42
42 kg block of copper from
25.0 °C to 88.5 °C?
A 547 J
A. q  m  s  t
B. 1.37 × 104 J t  (88.5  25.0) C
C. 3.47 × 104 J
J
D. 34.7 J q  1 420 g  0.385  63 .5 
C
g C
E. 4.74 × 104 J

Direction of Heat Flow
 Heat = energy transferred
f dbbetween 2 objects
b
 Heat lost by one object same magnitude as heat
gained
i d by
b other
h object
bj
 Sign of q indicates direction of heat flow
 Heat is gained, q is positive (+)
 Heat is lost, q is negative (–)
q1 = –q2
Ex. A piece of warm iron is placed into beaker of
cool water. Iron loses 10.0 J of heat, water gains
10.0 J of heat
qiron = – 10.0 J qwater = + 10.0 J
Your Turn!
A cast iron skillet is moved from a hot oven to a
sink full of water. Which of the following is
false?
A. The water heats
B The
B. Th skillet
kill t cools
l
C. The heat transfer for the skillet has a negative
( ) sign
(–) i
D. The heat transfer for the skillet is the same as
th h
the heatt ttransfer
f ffor th
the water
t
E. None of these are false

Ex. 1 Using Heat Capacity
A ball
b ll bearing
b i at 260 °C is i dropped
d d into
i a cup
containing 250. g of water. The water warms from
25 0 to 37
25.0 37.3
3 °C.
°C What is the heat capacity of the ball
bearing in J/°C?
Heat capacity of the cup of water = 1046J /°C
/ C
qlost by ball bearing = –qgained by water
1 Determine
1. D t i temperature
t t change
h off water
t
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
= 12,866 J
Ex. 1 Using Heat Capacity (cont)
A ball
b ll bearing
b i at 260 °C is i dropped
d d into
i a cup
containing 250. g of water. The water warms from
25 0 to 37
25.0 37.3
3 °C.
°C What is the heat capacity of the ball
bearing in J/°C? C of the cup of water = 1046J /°C
3 Determine
3. D t i how
h muchh heat
h t ball
b ll bearing
b i lost
l t
qball bearing = – qwater = –12,866 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
q  12,866 J
C   = 57.8 J/°C
t  222.7  C
Ex. 2: Specific Heat Calculation
How much energy must you lose from a 250. 250 mL
cup of coffee for the temperature to fall from
65 0°C to a 37
65.0°C 37.00 °C? {Assume density of coffee
= 1.00 g/mL, scoffee = swater = 4.18 J g1 °C1}
q = s  m  t
t = 37.0
37 0 – 65.0
65 0 °C = – 28.0
28 0 °C
q = 4.18 J g1 °C1250. mL1.00 g

g/mL(–
( 28.0 °C))
q = (–29.3  103 J) = –29.3 kJ

Ex. 3 Using Specific Heat
If a 38
38.66 g piece of gold absorbs 297 J of heat,heat
what will the final temperature of the gold be if the
initial temperature is 24
24.5 5 °C? The specific heat of
gold is 0.129 J g–1 °C–1.
Need to find tfinal t = tf – ti
First use q = s  m  t to calculate t
q 297 J
t   = 59.6 °C
s m 0.129 J  g 1  C 1  38.6 g
Next calculate tfinal
59.6 °C = tf – 24.5 °C
tf = 59.6 °C + 24.5 °C = 84.1 °C
Your Turn!
What is the heat capacity of a container if 100
100.g
g
of water (s = 4.18 J/g·°C) at 100.°C are added to
100 g of water at 25°C
100.g 25 C in the container and the
final temperature is 61°C?
A 35 J/°C
A.35
B.4.12 ×103 J/°C
C.21 J/°C
D.4.53 ×103 J/°C
/
E.50. J/°C
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Your Turn! - Solution
What is
Wh i the
h heat
h capacity
i off a container
i if 100.g
100 off
water (s = 4.18 J/g·°C) at 100.°C are added to 100.g
of water at 25°C in the container and the final
temperature is 61°C?
qlost
l t by
b hot t = m
h t water m∙tt∙ss
=(100.g)(61°C – 100.°C)(4.18 J/g·°C) = –16,302 J
qgained
i db by cold t = (100.g)(61
ld water (100 g)(61°C C – 25
25°C)(4
C)(4.18J/g
18J/g·°C)
C)
= 15,048 J
qlost
l t by
b system
t = 15,048
15 048 J + ((–1616,302
302 J) = –1254
1254 J
qcontainer = –qlost by system = +1254 J
q 1254 J
C   = 35 J/°C
t (61 - 25)  C
Chemical Bonds and Energy
Chemical bond
 Attractive forces that bind
 Atoms to each other in molecules, or
 Ions to each other in ionic compounds
 Give rise to compound’s potential energy
Chemical energy
 Potential energy stored in chemical bonds
Chemical reactions
 Generally involve both breaking and making
chemical bonds
Chemical Reactions
Forming Bonds
 Things that attract each other move closer together
 Decrease PE of reacting system
 Releases energy
 “Profits” of reaction
Breaking
g Bonds
 Things that are attracted to each other are forced
apart
 Increase PE of reacting system
 Requires
q energy
gy
 “Costs” of reaction
Exothermic Reaction
 Reaction where products have less chemical
energy than reactants
 Some
S chemical
h i l energy converted
t d to
t kinetic
ki ti energy
 Reaction releases heat to surroundings
 Heat leaves the system; q negative ( – )
 Heat/energy is product
 Reaction gets warmer (T)
Ex.
CH4(g) + 2O2(g)  CO2(g) + 2H2O(g) + heat

Endothermic Reaction
 Reaction where products have more chemical
energy than reactants
 Some kinetic energy converted to chemical energy
 Reaction absorbs heat from surroundings
g
 Heat added to system; q positive (+)
 Heat/energy is reactant
 Reaction becomes colder (T )
Ex. Photosynthesis
6CO2(g) + 6H2O(g) + solar energy 
C6H12O6(s) + 6O2(g)
Bond Strength
 Measure of how much energy is needed to
break bond or how much energy is released
when bond is formed.
formed
 Larger amount of energy = stronger bond
 Weak bonds require less energy to break than
strong bonds
 Key to understanding reaction energies
Ex. If reaction has
 Weak bonds in reactants and
 Stronger
g bonds in products
p
 Heat released
Why Fuels Release Heat
 Methane and oxygen have weaker bonds

 Water
W t and d carbon
b dioxide
di id have
h stronger
t bonds
b d
Your Turn!
Chemical energy is
A.the kinetic energy resulting from violent
d
decomposition
iti off energetic
ti chemicals.
h i l
B.the heat energy associated with combustion
reactions.
C.the electrical energy produced by fuel cells.
D.the potential energy which resides in chemical
bonds.
E.the energy living plants receive from solar
radiation.
ad at o

Heat of Reaction
 Amount off h
heat absorbed
b b d or released
l d in chemical
h l
reaction
 Determined
D i d by
b measuring
i temperature change
h
they cause in surroundings
C l i
Calorimeter
 Instrument used to measure temperature changes
 Container of known heat capacity
 Use results to calculate heat of reaction
Calorimetry
 Science of using calorimeter to determine heats of
reaction
Heats of Reaction
 Calorimeter design not standard
 Depends on
 Type of reaction
 Precision desired
 Usually measure heat of reaction under 1 of 2
sets of conditions
 Constant volume, qV
 C
Closed,
osed, rigid
g d container
co ta e
 Constant pressure, qP
 Open to atmosphere

What is Pressure?
 Amount of force acting on unit area
force
P
Pressure 
area
Atmospheric Pressure
 Pressure exerted by Earth’s atmosphere by virtue of
its weight.
g
 ~14.7 lb/in2
 Container open
p to atmosphere
p
 Under constant P conditions
 P ~ 14.7 lb/in
/ 2 ~ 1 atm ~ 1 bar

Comparing qV and qP
 Reactions involving large volume changes,
 Consumption or production of gas
 Difference between qV and qP can be significant
 Consider gas phase reaction in cylinder
immersed in bucket of water
 Reaction vessel is cylinder topped by piston
 Piston can be locked in place with pin
 Cylinder immersed in insulated bucket containing
weighed amount of water
 Calorimeter = piston,
piston cylinder,
cylinder bucket,
bucket and water

Comparing qV and qP
 Heat capacity of calorimeter = 8
8.101
101 kJ/°C
 Reaction run twice, identical amounts of reactants
Run 1: qV
 Run at constant volume
 Calorimeter absorbs all heat
produced in reaction
 Pin locked;
 ti = 24.00 C; tf = 28.91 C
qCal = Ct
/  ((28.91 – 24.00)C
= 8.101J/C ) = 39.8 kJ
qV = – qCal = –39.8 kJ
Calculating difference in qV and qP
Run 2: qP
 Run at atmospheric pressure
 Pin unlocked
27 32 C; tf = 31.54
 ti = 27.32 31 54 C
 Heat absorbed by calorimeter is
qCal = Ct
/  ((31.54  27.32)C
= 8.101J/C )
= 34.2 kJ
qP = – qCal = –34.2
–34 2 kJ

Why are qv and qp different in
reactions with significant volume
 qV = –39.8 kJ
change?
 qP = –34.2 kJ
 System (reacting mixture) expands
expands, pushes
against atmosphere, does work
 Uses
U up some energy that
th t would
ld otherwise
th i beb heat
h t
 Work = (39.8 kJ)  (34.2 kJ) = 5.6 kJ
 Expansion work or Pressure Volume work
 Minus sign
g means energy
gy leaving
g system
y

Work Convention
W k = –P×V
Work P×V
 P = opposing pressure against which piston
pushes
 V = change g in volume of gas
g during
g expansion
p
 V = Vfinal – Vinitial
 For Expansion
 Since Vfinal > Vinitial
 V must be positive
 So expansion work is negative
 Workk d
done by
b 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
17.0
0 atm
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
E.315

Your Turn!
A chemical reaction took place in a 6 liter cylindrical
enclosure fitted with a piston. Over the course of
the reaction
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
B.Work system.
C.The internal energy of the system increased.
D Th iinternal
D.The t l energy off the
th system
t d
decreased.
d
E.The internal energy of the system remained
unchanged.
h d
First Law of Thermodynamics
 In an isolated
l d system, the
h change
h in internall
energy (E) is constant:
 E = E f – Ei = 0
 Can
Can’tt measure internal energy of anything
 Can measure changes in energy
E is
i state
t t ffunction
ti
E = work + heat
E = q + w
E = heat input + work input

 “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 pprocesses, can predict
p
that their sum will be zero
 Some materials g
gain (have
( +)) energy
gy
 Others lose (have –) energy
 By monitoring surroundings,
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
i (+)
( ) W k done
Work d on system (IN)
w is (–) Work done by system (OUT)
Endothermic reaction
 E = +
Exothermic reaction
 E = –
E is Independent of Path
q and w
 NOT path
independent
 NOT state
functions
 Depend on
how change
takes place

Discharge of Car battery
ha
path
 Short out with wrench
 All energy converted to heat, no work
 E = q (w = 0)
path b
 Run
R motor
t
 Energy converted to work and little heat
 E = w + q (w >> q)
 E is same for each path
 Partitioning between 2 paths differs
Heat and Work
Two ways system can exchange
h internall energy
with surroundings
1. Heat
 Heat absorbed,, System’s
y E
 Heat lost, System’s E 
2 Work
2.
 Is exchanged when pushing force moves
something through distance
Ex. Compression or expansion of system’s gas

Heat and Work
2. Work
k (cont)
( )
 System
y does work on surroundings
g
 Pushes back an opposing force
System’ss E 
 System
Ex. Gases produced by combustion push piston
 System has work done on it by surroundings
 Surroundings
g push
p on system
y
 System’s E 
Ex Compression of system
Ex. system’ss gas

Heats of Reaction
 Measure E off system by
b measuring amount off
heat and work exchanged in system
 E = q + w
 Amount of work done by or on system depends on
 Pressure
 Volume
V l
 Heat of reaction measured under conditions of
either constant volume or constant pressure

Your Turn!
A gas releases
l 3.0 J off heat
h and
d then
h performs
f
12.2 J of work. What is the change in internal
energy off th
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
E30J
E.3.0

Your Turn!
Which of the following is not an expression for the
First Law of Thermodynamics?
A Energy
A. E is
i conservedd
B. Energy is neither created nor destroyed
C. The energy of the universe is constant
D. Energy can be converted from work to heat
E. The energy of the universe is increasing

Heat at Constant Volume, qV
 Carry out reaction in rigid walled container
 V = 0
 No work done
 All energy
gy comes out as heat
  E = q v – 0 = qv
 Heat of reaction at constant value
 Constant Volume calorimetry
 Used for combustion reactions
 Determine heat of combustion
 Bomb calorimeter
Bomb Calorimeter (Constant V)
 Apparatus for
measuring E in
reactions at constant
volume
 Vessel in center with
rigid walls
 Heavily
H il insulated
i l t d vatt
 Water bath
 No heat escapes
 E = qv

Ex. 3 Calorimeter Problem
When 1.000
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. a))
How many Calories 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 = 9.032kJ/°C
/ × 4.049 °C
= 36.57 kJ
qreleased by oil = – qcalorimeter = – 36.57 kJ
 36.57 kJ 1 kcal 1 Cal
q oil (in cal/g)   
1.000 g 4 184 kJ 1 kcal
4.184
–8.740 Cal/g oil
Ex. 3 Calorimeter Problem (cont)
b) Oli
Olive oilil is
i almost
l pure glyceryl
l l trioleate,
i l
C57H104O6. The equation for its combustion is
C57H104O6(ℓ) + 80 O2(g)  57 CO2(g) + 52 H2O(ℓ)
What is E for the combustion of one mole of
glyceryl trioleate (MM = 885.4 g/mol)? Assume the
olive oil burned in part a) was pure glyceryl
trioleate.
trioleate
 36.57 kJ 885.4 g C 57H104 O 6

1.000 g C 57H104 O 6 1 mol C 57H104 O 6
E = qV = –3.238
3 238 × 104 kJ/mol oil

Your Turn!
A bomb calorimeter has a heat capacity of 2.47
2 47 kJ/K.
kJ/K
When a 3.74×10–3 mol sample of ethylene (C2H4, MM
= 28.04
28 04 g/mol) was burned in this calorimeter,
calorimeter the
temperature increased by 2.14 K. Calculate the energy
y
of combustion for one mole of ethylene.
A. – 5.29 kJ/mol qcal = Ct
B. 5.29 kJ/mol = 2.47
2 47 kJ/K × 2.14
2 14 K = 5.286
5 286 kJ
C. – 148 kJ/mol
qethylene = – qcal = – 5.286 kJ
D – 1410 kJ/mol
D.
E. 1410 Kj/mol  5.286 kJ
E ethylene 
3.74  10  3 mol

Heat at Constant Pressure (qP)
 Chemists
h usually
ll do
d NOT run reactions at
constant V
 Usually do reactions in open containers
 Open
p to atmosphere;
p ; constant P
 Heat of reaction at constant Pressure (qP)
  E = qP + w
 Inconvenient
 Must
M t measure volume
l changes
h to i E
t determine
d t
 Define “corrected” internal energy for constant
pressure conditions
di i
Enthalpy (H)
 Heat off reaction at constant Pressure (qP)
H = E + PV
 Similar to E, but for systems at constant P
 Now have PV work + heat transfer
 H = state function
 At constant Pressure
H = E + PV = (qP + w) + PV
If only work is P–V work, w = – P V
H = (qP + w) – w = qP
Enthalpy Change (H)
H = 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
Enthalpy vs. Internal Energy
  H =  E + P V
Rearranging gives
  H –  E = P V
 Difference between H and E is PV
 Reactions where form or consume gases
 PV can be large
 Reactions involving only liquids and solids
 V negligible
 So H ≈ E

Measuring Energy Changes
 All forms of E can be converted quantitatively
into heat.
 Thus, can completely determine amount of
any form of E by converting it to heat.
How?
 1 way: Let heat flow from exothermic
reaction into mass of cooler water and
measure  T.
 To do this we need physical property of H2O
 Capacity of H2O to absorb heat

Coffee Cup Calorimeter
 Simple
 Measures qP
 Open to atmosphere
 Constant P
 Let heat flow from exothermic
reaction into mass of cooler
water and measure T
 Veryy little heat lost
 Calculate heat of reaction
 qP = Ct

Ex. 4 Coffee Cup Calorimetry
NaOH
N OH andd HCl undergo
d rapid
id and
d exothermic
h i reaction
i
when you mix 50.0 mL of 1.00 M HCl and 50.0 mL of
1 00 M NaOH.
1.00 NaOH The initial T = 25.5
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
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
fi l solution
l ti = 51.0
51 0 g + 52.0
52 0 g = 103.0
103 0 g
t = (32.2 – 25.5) °C = 6.7 °C
Ex. 4 Coffee Cup Calorimetry
qcal = 103.0
03 0 g  4.184
8 J g–11 °C–11  6.7
6 °C = 2887
288 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
0 0 00 moll HClCl
Heat evolved per mol HCl =
 2.9 kJ
H  = –58 kJ/mol
0.0500 mol HCl
Ex. 5: Coffee Cup Calorimetry
When 50.0
Wh 50 0 mLL off 0.987
0 987 M H2SO4 is
i added
dd d to 25.0
25 0 mLL
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 limiting reactant.
Assume: specific heat of the solution is 4.184 J/g
J/g°C,
C,
density is 1.00 g/mL, and the calorimeter absorbs a
negligible amount of heat.
Write balanced net ionic 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 = 75.0g×(33.9 – 25.0)°C×4.184J/g°C = 2.8×103J
Ex 5: Determine Limiting Reagent
1 L H2 SO 4 0.987 mol H2 SO 4
50.0 mL H2 SO 4  
1000 mL H2 SO 4 1 L H2 SO 4
= 0.04935 mol H2SO4 present
2 mol NaOH
0 04935 mol H2 SO 4 
0.049 = 0.0987
0 0987 mol NaOH
1 mol H2 SO 4 needed
1 L NaOH 2 mol NaOH
25.0 mL NaOH  
1000 mL NaOH 1 L NaOH
= 0.0500
0 0500 mol NaOH present
NaOH is limiting
2 8  10 3 J
 2.8 1 kJ
H   = – 56 kJ/mol
0.0500 mol NaOH 1000 J
Your Turn!
A 43.29
43 29 g sample of solid is transferred from boiling
water (T = 99.8°C) to 152 g water at 22.5°C in a
coffee cup
cup. The temperature of the water rose to
24.3°C. Calculate the specific heat of the solid.
A – 1.1
A. 1 1 × 103 J g–1 °C
C–1 q = m × s × t
B.1.1 × 103 J g–1 °C–1 4.184 J
C10J
C.1.0 g–1 °C–1
qwater  152g   24.3  22.5 
C
g C
D.0.35 J g–1 °C–1 = 1.1 × 103 J
E.0.25 J g–1 °C–1 qsample = – qwater = – 1.1 × 103 J
 1.1  10 3 J
s 
43.29 g  (24.3 – 99.8)  C
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
S
Standard
d dC Conditions
di i ffor H 's
'
 25 °C and 1 atm
Standard Heat of Reaction (H°)
 Enthalpy
py change
g for reaction at 1 atm and 25 °C
Ex. 5
N2(g) + 3H2(g) 
 2 NH3(g)
1.000 mol 3.000 mol 2.000 mol
 When
Wh N2 and
d H2 reactt tto fform NH3 att 25 °C and
d 1 atm
t
 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
 Hrxn different for different states
CH4(g) + 2O2(g)  CO2(g) + 2H2O(ℓ) H = – 890.5 kJ
CH4(g) + 2O2(g)  CO2(g) + 2H2O(g) H = – 802.3 kJ
 Difference = energy to vaporize water

Thermochemical Equation
 Write H° immediately after equation
N2(g) + 3H2(g)  2NH3(g) H°= – 92.38 kJ
 Assumes coefficients = # moles
92 38 kJ released  2 moles of NH3 formed
 92.38
 If 10 mole of NH3 formed
5N2(g) + 15H2(g)  10NH3(g) H°= – 461.9
461 9 kJ
 H°rxn = (5 × –92.38 kJ) = – 461.9 kJ
 Can
C have
h fractional
f l coefficients
ff
 Fraction of mole, NOT fraction of molecule
½N2(g) + 3/2H2(g)  NH3(g) H° = – 46.19 kJ
State Matters!
C3H8(g) + 5O2(g) → 3 CO2(g) + 4 H2O(g)
ΔH = – 2043 kJ
C3H8(g) + 5O2(g) → 3 CO2(g) + 4 H2O(ℓ)
ΔH = – 2219 kJ
Note: there is difference in energy because
states do not match
If H2O(ℓ) → H2O(g) ΔH = 44 kJ/mol
4H2O(ℓ) → 4H2O(g) ΔH = 176 kJ/mol
Or – 2219 kJ + 176 kJ = – 2043 kJ

Learning Check:
Consider the following reaction:
2C2H2(g) + 5O2(g) → 4CO2(g) + 2H2O(g)
ΔE = –2511 kJ
The reactants (acetylene and oxygen) have 2511
kJ more energy than products. How many kJ
are released
l d for
f 1 moll C2H2?
 2511kJ
 1mol C 2H2  –1,256 kJ
2mol C 2H2

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 = 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 CO2 can be
converted to glucose?
6mol CO 2 44.0g CO 2
100kJ    9.38 g
2816kJ 1mol CO 2

Your Turn!
Based on the reaction
CH4(g) + 4Cl2(g)  CCl4(g) + 4HCl(g)
H = – 434 kJ/mol CH4
What energy
gy change
g occurs when 1.2 moles of
methane reacts?
A.– 3.6 × 102 kJ
A. H = – 434 kJ/mol
/ × 1.2 mol
B.+5.2 × 102 kJ H = – 520.8 kJ
C 4.3
C.– 4 3 × 102 kJ
D.+3.6 × 102 kJ
E.– 5.2 × 102 kJ
Running Thermochemical
E
Equations
ti in
i Reverse
R
Consider
CH4(g) + 2O2(g)  CO2(g) + 2H2O(g)
H° = – 802.3
802 3 kJ
 Reverse thermochemical equation
 Must change sign of H
CO2(g) + 2H2O(g)  CH4(g) + 2O2(g)
H° = 802.3 kJ

Reverse Thermochemical
equation,
ti Changes
Ch sign
i off H
 Makes sense:
 Get energy out when form products
 Must
M st p
putt ene g in to go back to reactants
energy eactants
 Consequence of Law of Conservation of
Energy
 Like mathematical equation
 If you know H° for reaction, you also know H°
for reverse reaction

Multiple Paths; Same H°
 Can often get from reactants to products by
several different paths
Reactants Products
Intermediate A Intermediate B
Sh ld gett same H°

 Should
 Enthalpy is state function and path independent
 Let’s see if this is true
Ex. 7 Multiple Paths; Same H°
Path a: Single step
C(s) + O2(g)  CO2(g) H° = –393
393.5
5 kJ
Path b: Two step
St 1
Step 1: C(s) + ½O2(g)  CO(g) H° = –110.5
110 5 kJ
Step 2: CO(g) + ½O2(g)  CO2(g) H° = –283.0 kJ
Net Rxn: C(s) + O2(g)  CO2(g) H° = –393.5 kJ
 Chemicallyy and thermochemically,
y, identical
results
 True for Exothermic reaction or for Endothermic
reaction
Ex.8 Multiple Paths; Same H°
Path a: N2(g) + 2O2(g)  2NO2(g) H° = 68 kJ
Path b:
Step 1: N2(g) + O2(g)  2NO(g) H° = 180. kJ
Step 2: 2NO(g) + O2(g)  2NO2(g) H° = –112
112 kJ
Net rxn: N2(g) + 2O2(g)  2NO2(g) H° = 68 kJ
Hess’s Law of Heat Summation
 For anyy reaction that can be written into steps,
p , value
of H° for reactions = sum of H° values of each
individual step

Enthalpy Diagrams
 Graphical description of Hess’ Law
 Vertical Axis = enthalpy scale
 Horizontal line =various states of reactions
 Higher up = larger enthalpy
 Lower down = smaller enthalpy

Enthalpy Diagrams
 Use to measure H
 Arrow down H = –
 Arrow up H = +
 Calculate cycle
 1 step process = sum
of 2 step process
Ex. H2O2(ℓ)  H2O(ℓ) + ½O2(g)

–286kJ 188kJ + Hrxn
286kJ = –188kJ
Hrxn = –286 kJ – (–188 kJ )
Hrxn = –98
98 kJ
Hess’s Law
Hess’s
’ Law off Heat Summation
i
 Going from reactants to products
 Enthalpy change is same whether reaction takes
place in one step or many
 Chief Use
 C l l ti off H° for
Calculation f reaction
ti ththatt can’t
’t b
be
measured directly
 Th
Thermochemical
h i l equations
ti for
f individual
i di id l steps
t
of reaction sequence may be combined to obtain
thermochemical equation of overall reaction

Rules for Manipulating
Thermochemical Equations
1. When equation is reversed, sign of H° must
also be reversed.
q
2. If all coefficients of equation are multiplied
p or
divided by same factor, value of H° 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

Strategy for Adding Reactions
T
Together:
th
1. Choose most complex compound in equation
for one-step path
q
2. Choose equation in multi-step
p path
p that
contains that compound
3. Write equation down so that compound
 Is on appropriate side of equation
 has appropriate coefficient for our reaction
4. Repeat steps 1 – 3 for next most complex
compound etc.
compound, etc

Strategy for Adding Reactions (Cont.)
5. Choose equation that allows you to
 cancel intermediates
 multiply by appropriate coefficient
6 Add reactions together and cancel like terms
6.
7. Add energies together, modifying enthalpy
values
l in
i same way equation
ti modified
difi d
 If reversed equation, change sign on enthalpy
 If doubled equation, double energy

Ex.9 Calculate H° for
Cgraphite(s)  Cdiamond(s)
Given Cgr(s) + O2(g)  CO2(g) H° = –394 kJ
–1[ Cdia(s) + O2(g)  CO2(g) H° = –396 kJ ]
 To gget desired equation,
q , must reverse 2nd
equation and add resulting equations
Cgr(s) + O2(g)  CO2(g) H° = –394
394 kJ
CO2(g)  Cdia(s) + O2(g) H° = –(–396 kJ)
Cgr(s) + O2(g) + CO2(g)  Cdia(s) + O2(g) + CO2(g)
H° = –394 kJ + 396 kJ = + 2 kJ

Learning Check: Ex.10
Calculate H° for
2 Cgr(s) + H2(g) 
 C2H2(g)
Given the following:
a. C2H2(g) + 5/2O2(g)  2CO2(g) + H2O(ℓ)
H° = – 1299.6 kJ
b. Cgr(s) + O2(g)  CO2(g) H° = –393.5 kJ
c. H2(g) + ½O2(g)  H2O(ℓ) H° = – 285.8 kJ

Ex.10 Calculate for
2Cgr (s) + H2(g)  C2H2(g)
–a 2CO2(g) + H2O((ℓ))  C2H2(g) + 5/2O2(g)

H° = – (–1299.6 kJ) = +1299.6 kJ
+2b 2Cgr(s) + 2O2(g)  2CO2(g)
H° =(2 –393.5 kJ) = –787.0 kJ
+c H2(g) + ½O2(g)  H2O(ℓ) H° = –285.8
285.8 kJ
2CO2(g) + H2O(ℓ) + 2Cgr(s) + 2O2(g) + H2(g) + ½O2(g)

 C2H2(g) + 5/2O2(g) + 2CO2(g) + H2O(ℓ)
2Cgr(s) + H2(g)  C2H2(g) H° = +226.8 kJ

Your Turn!
Which of the following is a statement of Hess's Law?
A.H for a reaction in the forward direction is equal to 
H for the reaction in the reverse direction
direction.
B.H for a reaction depends on the physical states of the
reactants and products
products.
C.If a reaction takes place in steps, H for the reaction
will be the sum of Hs for the individual steps.
steps
D.If you multiply a reaction by a number, you multiply
H by the same number.
E.H for a reaction in the forward direction is equal in
g
magnitude and opposite
pp g to H for the reaction in
in sign
the reverse direction.
Your Turn!
Given the following data:
C2H2(g) + O2(g)  2CO2(g) + H2O(ℓ) H = –1300. kJ
C(s) + O2(g)  CO2(g) H = –394
394 kJ
H2(g) + O2(g)  H2O(ℓ) H = –286 kJ
C l l t for
Calculate f theth reaction
ti
2C(s) + H2(g)  C2H2(g)
A.226 kJ
B.–1980 kJ
H = +1300.
+1300 kJ + 2(–394
2( 394 kJ) + (–286
( 286 kJ)
C.–620 kJ
D.–226 kJ
E.620 kJ
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 anyy 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) std states = 0
C Cgr(s)
H H2(g) Forming
F i element
l t
from itself.
Al Al(s)
Ne Ne(g)
 See Appendix C in back of textbook and Table 7.2
72

Uses of Standard Enthalpy (Heat)
Formation, Hf°
of Formation
1. From definition of Hf°, can write balanced
equations directly
Hf°{C2H5OH(ℓ)}
2C(s, gr) + 3H2(g) + ½O2(g)  C2H5OH(ℓ)
Hf° = –277.03 kJ/mol
Hf°{Fe2O3(s)}
2Fe(s) + 3/2O2(g)  Fe2O3(s) Hf° = – 822.2 kJ/mol
/

Your Turn!
What is the reaction that corresponds to the
standard enthalpy of formation of NaHCO3(s), Hf°
= – 947.7
947 7 kJ/mol?
a.Na(s) + ½H2(g) + 3/2O2(g) + C(s, ggr)  NaHCO3(s)

b.Na+(g) + H+(g) + 3O2–(g) + C4+(g)  NaHCO3(s)
Na+(aq) + H+(aq) + 3O2–(aq) + C4+(aq)  NaHCO3(s)
cc.Na
d.NaHCO3(s)  Na(s) + ½H2(g) + 3/2O2(g) + C(s, gr)
Na+(aq) + HCO3–(aq)  NaHCO3(s)
e.Na
e

Using Hf°
2. Way to apply Hess’s Law without needing to
2
manipulate thermochemical equations
Sum of all Sum of all

H°reaction = H°f of all of – H°f of all of
the products the 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)}
)}

Ex.11 Calculate H°rxn Using Hf°
Calculate H°rxn using Hf° data for the reaction
SO3(g)  SO2(g) + ½O2(g)
1.Add Hf° for each product times its coefficient
2 Subtract Hf° for each reactant times its
2.Subtract
coefficient.
H rxn

 H f (SO 2 ( g ))  1
2 H 
f (O 2 ( g ) )  H 
f (SO 3 ( g ))
H rxn

 297 kJ/mol
/  1
2 (0 )  (396 kJ/mol)
kJ/mol)
/ / )
H°rxn = 99 kJ/mol

Learning Check
Calculate H°rxn using Hf° for the reaction
4NH3(g) + 7O2(g)  4NO2(g) + 6H2O(ℓ)
H rxn

 4 H f (NO 2 ( g ))  6 H f (H2 O())
 
 4 H f (NH 3 ( g ))  7 H f (O 2 ( g ))
H rxn

 4 mol(34 kJ/mol)  6 mol( 285.9 kJ/mol)
 4 mol(  46.0 kJ/mol)  7 mol(0 kJ/mol)
H°rxn = [136 – 1715.4
1715 4 + 184] kJ
H°rxn = – 1395 kJ

Check Using Hess’s Law
*[ 3(g)  ½ N2(g) + 3/2 H2(g)] – 4*Hf°(NH3, g)
4*[NH
7*[ O2(g)  O2(g) ] – 7*Hf°(O2, g)
4*[ O2(g) + ½ N2(g)  NO2(g)] 4*Hf°(NO2, g)
6*[[ H2(g) + ½ O2(g)  H2O(ℓ) ] 6
6 6* Hf°(H2O, ℓ)
4NH3(g) + 7O2(g)  4NO2(g) + 6H2O((ℓ))

H rxn

 4 H f (NO 2 ( g ))  6 H f (H2 O())
 
 4 H f (NH3 ( g ))  7 H f (O 2 ( g ))
Same as before

Other Calculations
 Don’t always want to know H°rxn
 Can use Hess’s Law and H°rxn to calculate
Hf° for
f compound d where
h nott kknown
Ex. Given the following data

Ex data, what is the value of
Hf°(C2H3O2–, aq)?
Na+(aq) + C2H3O2–(aq) + 3H2O(ℓ)  NaC2H3O2·3H
3H2O(s)
H°rxn = –19.7 kJ/mol
Hf°(Na+, aq) – 239.7
239 7 kJ/mol
Hf°(NaC2H3O2·3H2O, s) – 710.4 kJ/mol
Hf°(H2O,
O ℓ) – 285.9
285 9 kJ/mol
kJ/ l
Ex. 13 cont.
H°rxn = Hf°(NaC2H3O2·3H2O, s) – Hf°(Na+, aq)
– Hf°(C2H3O2–, aq) – 3Hf°(H2O, ℓ)
Rearranging
Hf°(C2H3O2–, aq) = Hf°(NaC2H3O2·3H
3H2O, s) –
Hf°(Na+, aq) – H°rxn – 3Hf° (H2O, ℓ)
Hf°(C2H3O2–, aq) =
–710.4kJ/mol – (–239.7kJ/mol) – (–19.7kJ/mol)
– 3(
3(–285
285.9kJ/mol)
9kJ/mol)
= + 406.7 kJ/mol

Learning Check
Calculate H for this reaction using Hf° data.
data
2Fe(s) + 6H2O(ℓ)  2Fe(OH)3(s) + 3H2(g)
Hf° 0 –285.8 –696.5 0
H°rxn = 2*Hf°(Fe(OH)
°(F (OH)3, s) + 3*Hf°(H2, g)
– 2* Hf°(Fe, s) – 6*Hf°(H2O, ℓ)
H°rxn = 2 mol*(–
l*( 696.5
696 5 kJ/mol)
kJ/ l) + 3*0 – 2*0
– 6 mol*(–285.8 kJ/mol)
H°rxn = –1393 kJ + 1714.8 kJ
H°rxn = 321.8 kJ

Learning Check
Calculate
C l l H for h reaction using Hf° d
f this data.
CO2(g) + 2H2O(ℓ)  2O2(g) + CH4(g)
Hf° –393.5 –285.8 0 – 74.8
H°rxn = 2*Hf°(O2, g) + Hf°(CH4, g)

–Hf°(CO
( O2, g) – 2* Hf°(H
( 2O, ℓ)
H°rxn = 2×0 + 1 mol × (–74.8 kJ/mol) – 1 mol
× ((–393.5
393.5 kJ/mol) – 2 mol × ((–285.8
285.8 kJ/mol)
H°rxn = –74.8 kJ + 393.5 kJ + 571.6 kJ
H°rxn = 890.3
890 3 kJ

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Chapter

Chemistry: The Molecular Nature

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

A.A pencil rolls across a desk

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 4

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

A.A book is raised 6 feet above the floor.

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

Total = Potential + Kinetic

 If calculated value is greater than 1000 J, use

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

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 12

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 13

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 22

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

 Process where neither energy nor

A.include the surroundings.

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

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

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 36

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

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 43

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 45

q = 4.18 J g1 °C1250. mL1.00 g

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 48

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

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 54

 Methane and oxygen have weaker bonds

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 58

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 60

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 61

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 62

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 64

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 65

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 67

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 69

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 70

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

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 72

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 74

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 75

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 76

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 77

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 78

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 80

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 82

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 83

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 87

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 88

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 89

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 95

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 97

Or – 2219 kJ + 176 kJ = – 2043 kJ

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 100

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 101

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 103

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 104

Sh ld gett same H°

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 107

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 108

Ex. H2O2(ℓ)  H2O(ℓ) + ½O2(g)

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 110

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 111