Chapter
Seven
Thermodynamics:
The
First
Law
CHEM
1211K
Fall
2013
Objec;ves
At
the
end
of
this
chapter
you
will
be
able
to:
Understand
and
calculate
heat
and
work
Understand
the
principles
behind
expansion
work
Explore
the
measurement
of
heat
Explore
heat
transfer
at
constant
pressure
and
heat
capacity
at
constant
pressure
and
constant
volume
Understand
the
enthalpy
of
physical
change
and
interpret
heaFng
curves
Explore
the
relaFonship
between
enthalpy
and
internal
energy
Understand
and
use
standard
reacFon
enthalpies
and
enthalpies
of
formaFon.
Key
Ideas
Heat
and
work
are
equivalent
ways
of
transferring
energy
between
a
system
and
its
surroundings.
The
total
energy
of
an
isolated
system
is
constant.
The
enthalpy
change
for
a
process
is
equal
to
the
heat
released
at
constant
pressure.
Why
is
it
important?
The
laws
of
thermodynamics
govern
chemistry
and
life.
They
explain
why
reacFons
take
place
and
let
us
predict
how
much
heat
reacFons
release
and
how
much
work
they
can
do.
Thermodynamics
plays
a
role
in
every
part
of
our
lives.
The
energy
released
as
heat
can
be
used
to
compare
fuels,
and
the
energy
resources
of
food
are
used
to
assess
its
nutriFonal
value.
4
Introduc;on
Thermodynamics
is
the
study
of
the
transformaFons
of
energy
from
one
form
into
another.
The
rst
law
of
thermodynamics
Keeps
track
of
energy
How
much
energy
a
reaction
produces
or
is
needed
to
occur
The
second
law
of
thermodynamics
Explains
why
some
reactions
take
place
why
others
do
not
spontaneity
of
reactions
5
Introduc;on
Two
fundamental
concepts
of
thermodynamics
are
heat
(q)
and
work
(w).
These
are
two
forms
of
energy
Systems
(7.1)
To
keep
track
of
changes
in
energy,
we
divide
the
world
into
two
parts:
System
region
of
interest
Example:
chemical
reaction
-Surroundings
everything
besides
the
system
Example:
water
bath
Note:
in
aqueous
reactions,
water
is
part
of
the
surroundings
System
+
surroundings
=
universe
Figure 7.3
Systems
(7.1)
A
system
can
be:
Open
can
exchange
both
matter
and
energy
with
the
surroundings
Example:
human
body
Closed
Bixed
amount
of
matter
but
can
exchange
energy
with
the
surroundings
Example:
hot
or
cold
pack
Isolated
no
contact
with
its
surroundings;
can
exchange
neither
matter
nor
heat
Example:
liquid
inside
sealed
thermally
insulated
vacuum
Blask
Figure 7.4
Systems
(7.1)
SecFon
summary:
In
thermodynamics,
the
universe
consists
of
a
system
and
its
surroundings.
An
open
system
can
exchange
both
ma>er
and
energy
wit
the
surroundings.
A
closed
system
can
exchange
only
energy.
An
isolated
system
can
exchange
nothing.
Unless
speci*ied
otherwise
we
will
be
working
from
the
perspective
of
the
system
9
Work
and
Energy
(7.2)
Work
(w)
is
the
process
of
achieving
moFon
against
an
opposing
force.
Work
=
opposing
force
x
distance
moved
w
=F
x
d
force
is
measured
in
newtons
(1
N
=
1kgm/s2)
Force
x
distance
=
(1kgm/s2)(m)=
kgm2/s2
1
kgm2/s2=
1
Joule;
unit
of
energy
10
Work
and
Energy
(7.2)
Energy
is
the
capacity
of
a
system
to
do
work
(at
least,
thats
one
deniFon
of
it!).
A
system
that
can
do
a
lot
of
work
possesses
a
lot
of
energy
A
system
can
do
work
on
its
surroundings
When
this
occurs
the
capacity
the
system
has
to
do
work
reduces;
energy
is
decreased;
w
<
0,
value
of
work
is
negative
The
surroundings
can
do
work
on
the
system
When
this
occurs
the
capacity
the
system
has
to
do
work
increases;
energy
is
increased
w
>
0,
value
of
work
is
positive
The
total
store
of
energy
in
a
system
is
called
its
internal
energy
(U).
U
=
q
+
w
11
Work
and
Energy
(7.2)
Throughout
thermodynamics:
X
=
Xnal
-
XiniFal
X
represents
difference
in
the
property
of
X
If
X
has
a
negative
value
then
the
property
decreased
U
=
Unal
-
UiniFal
From
the
perspective
of
the
system:
U
is
positive,
U>
0
then
the
internal
energy
increases
U
is
negative,
U<
0
then
the
internal
energy
decreases
12
Work
and
Energy
(7.2)
U
=
q
+
w
If
no
other
type
of
transfer
of
energy
takes
place
besides
work,
then:
q=0
and
U
=
w
13
Work
and
Energy
(7.2)
SecFon
summary:
Work
is
the
transfer
of
energy
to
a
system
by
a
process
that
is
equivalent
to
raising
or
lowering
a
weight.
For
work
done
on
a
system,
w>0
(w
=
+)
For
work
done
by
a
system,
w<0
(w
=
-)
The
internal
energy
of
a
system
may
be
changed
by
doing
work.
In
the
absence
of
other
changes,
U
=
w.
14
Expansion
Work
(7.3)
Two
types
of
work:
Expansion
work
work
arising
from
change
in
volume
of
system
Figure 7.5
Simplest
example
is
work
done
by
or
on
a
system
consisting
of
a
gas
in
a
cylinder.
w=
F
x
d
F
=
Pressure
x
Area
w
=
Pressure
x
Area
x
d
w
=
-PexV
(at
constant
external
P)
The
negative
is
present
for
sign
convention
1L
atm
=
101.325
J
15
Expansion
Work
(7.3)
Two
types
of
work:
Nonexpansion
work
work
that
does
not
involve
a
change
in
volume
of
the
system
Chemical
reaction
in
a
battery
can
do
work
by
causing
an
electrical
current
to
Blow
16
Heat
(7.4)
Remember:
there
are
two
terms
that
are
used
to
determine
internal
energy
of
a
system
The
internal
energy
of
a
system
is
the
capacity
of
that
system
to
do
work
and
the
capacity
for
the
system
to
transfer
heat
The
internal
energy
of
a
system
can
also
be
changed
by
transferring
energy
to
or
from
the
surroundings
as
heat.
Heat
energy
transferred
as
a
result
of
a
temperature
difference
17
Heat
(7.4)
Heat
is
energy
in
transiFon
as
a
result
of
a
temperature
dierence.
Heat
and
temperature
are
NOT
the
same
thing!
This
temperature
dierence
arises
from
the
energy
of
thermal
moFon.
Molecules
at
higher
temperature
have
a
greater
kinetic
energy
than
molecules
at
a
lower
temperature
Example:
Two
regions
of
molecules
with
different
kinetic
energies
are
brought
together
Region
of
molecules
with
greater
kinetic
energy
bump
into
region
with
less
kinetic
energy
and
transfer
kinetic
energy
Region
that
lost
kinetic
energy
decreases
in
temperature
Region
that
gained
kinetic
energy
increases
in
temperature
18
Heat
(7.4)
Energy
transferred
as
heat
is
denoted
as
q.
U
=
q
+
w
and
w
=
0
If
the
internal
energy
of
the
system
is
changed
by
transferring
energy
as
heat
(and
no
other
processes
take
place,
such
as
work,)
U
=
q.
w
=
0,
when
there
is
no
change
in
volume,
at
constant
pressure
When
heat
is
lost
from
the
system,
q
<
0,
q
is
negaFve
When
the
system
gains
heat,
q
>
0,
q
is
posiFve
19
Heat
(7.4)
Like
any
form
of
energy,
heat
is
oben
measured
in
Joules.
1
J
=
kgm2/s2
Other
units
of
measurement:
calorie
1
calorie
(cal)
=
4.184
J
Calorie
1
Calorie
(Cal)
=
1000
calorie
=
1
nutritional
calorie
20
Heat
(7.4)
Exothermic
processes
are
those
that
release
heat
into
the
surroundings.
Endothermic
processes
absorb
heat
from
the
surroundings.
Figure 7.9
21
Heat
(7.4)
SecFon
summary:
Heat
is
the
transfer
of
energy
as
a
result
of
a
temperature
dierence.
When
energy
is
transferred
as
heat
and
no
other
processes
occur,
U
=
q.
When
energy
enters
a
system
as
heat,
q>0
(posiOve).
When
energy
leaves
a
system
as
heat,
q<0
(negaOve).
22
The
Measurement
of
Heat
(7.5)
An
inux
of
energy
into
a
system
typically
raises
the
temperature
of
the
system.
To
convert
a
temperature
change
into
energy,
we
need
to
know
the
heat
capacity:
The
amount
of
heat
needed
to
cause
a
speciBic
T
in
a
given
amount
of
substance
ratio
of
heat
supplied
to
T
produced
heat supplied
Heat capacity =
temperature rise produced
q
C=
T
23
The
Measurement
of
Heat
(7.5)
If
heat
capacity
is
known,
then
the
amount
of
heat
supplied
can
be
calculated:
q
=
CT
Heat
capacity
is
a
extensive
propertyit
depends
on
the
amount
of
mafer
present.
Specic
heat
capacity
(speci*ic
heat)
Cs
amount
of
heat
needed
to
raise
the
temperature
1.0
g
of
a
substance
1C
Units:
J/gC
Molar
heat
capacity
Cm
amount
of
heat
needed
to
raise
the
temperature
1.0
mol
of
a
substance
1
degree
Units:
J/molK
24
The
Measurement
of
Heat
(7.5)
The
energy
supplied
as
heat
to
a
substance
can
be
calculated
from
mass,
specic
heat
capacity,
and
change
in
temperature.
q
=
mCsT
Looking
at
units:
q
=
(g)(J/gC)(C)=
J
Similarly:
q
=
nCmT
Looking
at
units:
q
=
(mols)(J/molK)(K)=
J
25
The
Measurement
of
Heat
(7.5)
Keep
in
mind
that
the
soluGon
of
which
the
temperature
change
is
being
measured
is
part
of
the
surroundings,
and
the
system
is
closed.
Increase
in
soluFon
temperature
Heat
was
released
by
the
system
to
the
surroundings.
The
reacFon
is
exothermic.
Decrease
in
soluFon
temperature
Heat
was
absorbed
by
the
system
from
the
surroundings.
The
reacFon
is
endothermic.
26
The
Measurement
of
Heat
(7.5)
Example:
Calculate
the
nal
temperature
of
a
200.0
g
sample
of
stainless
steel
at
25.0oC
aber
743
J
of
heat
have
been
provided
to
the
system.
Cs
for
stainless
steel
=
0.51
J/goC.
q = mCs T
Find
T
Find
Tinitial
T = Tfinal Tinitial
+743J = (200.0 g) (0.51J/gC)T
T = 7.284C
7.284C = Tfinal 25.00C
Tfinal = 32.3C
27
The
Measurement
of
Heat
(7.5)
Transfers
of
energy
as
heat
are
measured
with
a
calorimeter.
qcal
=
CcalT
Ccal
is
the
heat
capacity
of
the
calorimeter
Each
calorimeter
is
slightly
different
and
has
a
different
ability
to
absorb
heat
Calorimeters
have
to
be
calibrated
to
determine
the
amount
of
heat
each
absorbs
Figure 7.11
28
The
Measurement
of
Heat
(7.5)
When
determining
the
changes
in
heat
in
a
system
and
the
surroundings,
qsystem
=
-qsurroundings
And:
qsystem
=
-[qcal
+
qsurroundings
]
29
The
Measurement
of
Heat
(7.5)
Example:
100.0
grams
of
H2O(l)
at
100C
is
mixed
with
82.00
g
of
H2O(l)
at
65.0
C.
What
is
the
nal
temperature
of
the
mixture?
The
specic
heat
of
H2O(l)
=
4.184
J/gC.
Find
how
hot
and
cool
solutions
are
related
qhot = qcold
Solve
for
Binal
temp.
of
mixture
Binal
temp.
is
same
for
both
H2O
-mhot Cs Thot = mcold Cs Tcold
-mhot Cs (Tf Tihot ) = mcold Cs (Tf Ticold )
-(100.0g)(4.184J/gC)(Tf 100C) = (82.00g)(4.184J / gC)(Tf 65.00C)
Tf = 84.2C
30
The
Measurement
of
Heat
(7.5)
Example:
A
small
piece
of
calcium
carbonate
was
placed
in
a
calorimeter
with
Ccal
=
487.6
J/oC
along
with
100.0
mL
of
hydrochloric
acid.
The
temperature
of
the
calorimeter
rose
by
3.57oC.
What
is
the
value
of
U
for
this
reacFon?
U
=
q
+
w
,
w
=
0
U
=
q
q
=
-qcal
q = -CcalT
q = -[(487.6J / C)(3.57C)]
q = -1740 J
Check
sign
of
q
with
increase
or
decrease
of
heat
in
system
Temperature
increases,
energy
leaves
the
system
in
form
of
heat,
negative
q
31
The
Measurement
of
Heat
(7.5)
SecFon
summary:
The
heat
capacity
of
an
object
is
the
raOo
of
the
heat
supplied
to
the
temperature
rise
produced.
Heat
transfers
are
measured
by
using
a
calibrated
calorimeter.
32
The
First
Law
(7.6)
In
many
processes,
the
internal
energy
changes
as
a
result
of
BOTH
work
and
heat.
U
=
q
+
w
The
transfer
of
energy
as
heat
or
work
on
or
by
a
system
do
not
have
to
be
separate
entities;
they
can
occur
at
the
same
time
Heat
energy
can
be
transferred
to
work
energy
and
vice
versa
Figure 7.13
33
The
First
Law
(7.6)
Example:
A
system
was
heated
using
400.0
J
of
heat,
and
its
internal
energy
increased
by
150.0
J.
Calculate
w.
Was
work
done
on
the
system
or
by
the
system?
System
gained
heat
q,
positive
value
Internal
energy
increased
U,
positive
value
U = q + w
+150.0J = + 400.0J + w
250.0J = w
System
performs
work
on
the
surroundings
Work
is
a
negative
value
34
The
First
Law
(7.6)
The
rst
law
of
thermodynamics
states
that
the
internal
energy
of
an
isolated
system
is
constant.
35
The
First
Law
(7.6)
Internal
energy
is
a
state
funcGon
,
a
property
that
depends
only
on
the
current
state
of
the
system
and
is
independent
of
how
that
state
was
prepared.
Other
state
funcFons:
P,
V,
T,
and
density
Work
and
heat
(w
and
q)
are
NOT
state
funcOons.
36
The
First
Law
(7.6)
Figure 7.14
State
function:
(a)
take
any
path
between
two
speciBic
spots
on
the
mountain,
but
the
difference
in
altitude
between
the
two
will
always
be
equal
(independent
of
the
path
taken)
(b)
The
pathway
between
the
two
systems
shown
is
different
but
the
difference
in
internal
energy
will
be
the
same.
37
The
First
Law
(7.6)
SecFon
summary:
The
rst
law
of
thermodynamics
states
that
the
internal
energy
of
an
isolated
system
is
constant.
A
state
funcOon
depends
only
on
the
current
state
of
a
system.
The
change
in
a
state
funcOon
between
two
states
is
independent
of
the
path
between
them.
Internal
energy
is
a
state
funcOon
but
work
and
heat
are
not.
38
Heat
Transfers
at
Constant
Pressure
(7.8)
Enthalpy,
H
is
a
state
funcFon
that
allows
us
to
keep
track
of
energy
changes
at
constant
pressure.
H
=
U
+
PV
At
constant
pressure:
H
=
U+
PV
Still,
U=
q+
w
and
w
=
-PV:
H
=
q
PV
+
PV
H
=
qp
39
Heat
Transfers
at
Constant
Pressure
(7.8)
A
change
in
the
enthalpy
of
a
system
is
equal
to
the
heat
released
or
absorbed
at
constant
pressure.
H
>
0
endothermic
H
<
0
exothermic
40
Heat
Transfers
at
Constant
Pressure
(7.8)
Example:
In
a
given
reacFon
at
constant
pressure,
45
kJ
of
energy
leb
the
system
as
heat
and
30.
kJ
of
energy
leb
the
system
as
expansion
work.
What
are
the
values
of
H
and
U
for
this
process?
Is
the
reacFon
endothermic
or
exothermic?
Heat
was
removed
from
the
system
H
is
a
negative
value
H = q p
H = -45 kJ, exothermic
System
performs
expansion
work
on
the
surroundings
Work
is
a
negative
value
U = q + w
U = -45kJ + (30. kJ )
U = 75 kJ
41
Heat
Transfers
at
Constant
Pressure
(7.8)
SecFon
summary:
The
change
in
enthalpy
of
a
system
is
equal
to
the
heat
supplied
to
the
system
at
constant
pressure.
For
an
endothermic
process,
H
>
0.
For
an
exothermic
process,
H
<
0.
42
Heat
Capaci;es
at
Constant
Volume
and
Constant
Pressure
(7.9)
Heat
capaciFes
depend
on
the
condiFons
under
which
the
heaFng
takes
place.
Molar
heat
capacity
at
constant
volume:
q
Cm =
T
U = q + w
Work
=
0
at
constant
volume,
U = q
U
CV ,m =
T
Units
of
CV,m:
J/molK
43
Heat
Capaci;es
at
Constant
Volume
and
Constant
Pressure
(7.9)
Heat
capaciFes
depend
on
the
condiFons
under
which
the
heaFng
takes
place.
Molar
heat
capacity
at
constant
pressure:
q
CP =
T
Work
=
0
at
constant
pressure,
H = q
H
CP,m =
T
Units
of
CP,m:
J/molK
44
Heat
Capaci;es
at
Constant
Volume
and
Constant
Pressure
(7.9)
CV,m
and
CP,m
have
very
similar
values
for
a
given
solid
or
a
specic
liquid.
values
are
NOT
very
similar
for
gases
Example:
CV,m
and
CP,m
values
are
similar
for
H2O(l)
but
not
for
H2O(g)
When
heated,
gases
expand
more
than
liquids
and
solids
More
energy
is
lost
in
the
form
of
work
when
heated
at
constant
pressure
45
A
Molecular
Interlude:
The
Origin
of
the
Heat
Capaci;es
of
Gases
(7.10)
Atoms
and
molecules
can
store
energy
as
translaFonal,
rotaFonal
and
vibraFonal
energy.
Atoms
Linear
molecules
Non-linear
molecules
CV,m
(3/2)R
(5/2)R
3R
CP,m
(5/2)R
(7/2)R
4R
R
=
8.314
J/molK
Example:
Can
use
in
q
=
mCV,mT
type
calculations.
46
Heat
Capaci;es
at
Constant
Volume
and
Constant
Pressure
(7.9)
SecFon
summary:
The
molar
heat
capacity
of
an
ideal
gas
at
constant
pressure
is
greater
than
that
at
constant
volume.
47
The
Enthalpy
of
Physical
Change
(7.11)
What
actually
happens
when
a
solid
melts?
When
a
liquid
evaporates?
All
phase
changes
have
a
heat
Blow
associated
with
them.
Some
are
endothermic
Some
are
exothermic
48
The
Enthalpy
of
Physical
Change
(7.11)
Phase
changes
that
increase
molecular
contact
are
Exothermic
.
Examples:
condensation,
freezing,
deposition
When
a
phase
transiFon
takes
place
at
constant
pressure,
the
heat
transfer
accompanying
the
phase
change
is
equal
to
the
change
in
enthalpy
of
the
substance.
qP
=
Hphase
change
49
The
Enthalpy
of
Physical
Change
(7.11)
Enthalpy
of
vaporizaGon,
Hvap
is
the
dierence
in
molar
enthalpy
between
the
vapor
and
the
liquid
states.
Hvap
=
Hm(vapor)
Hm(liquid)
Hm
molar
enthalpy
All
Hvap
are
positive
The
stronger
the
intermolecular
force
present
in
a
molecule,
the
greater
the
Hvap.
50
The
Enthalpy
of
Physical
Change
(7.11)
Example:
How
much
energy,
in
kJ,
is
needed
to
evaporate
50.0
g
H2O
if
Hvap
=
+
40.7
kJ/mol?
When
there
is
a
phase
change,
there
is
not
a
T
q p = (H )(amount)
q p = (40.7kJ / mol)(n)
q p = (40.7kJ / mol)(2.77mol)
$
! 50.0g H 2O $!
1 mol
& = 2.77mol H 2O
#
&#
"
%" 18.02 g H 2O %
q p = 113 kJ
51
The
Enthalpy
of
Physical
Change
(7.11)
Table 7.3
Hvap
>
Hfus
for
a
given
substance,
this
is
related
to
the
strength
of
intermolecular
forces
present
52
The
Enthalpy
of
Physical
Change
(7.11)
Enthalpy
of
fusion,
Hfus
is
the
enthalpy
change
accompanying
the
melFng
(fusion)
of
a
substance.
Hfus
=
Hm(liquid)
Hm(solid)
Endothermic
process
53
The
Enthalpy
of
Physical
Change
(7.11)
Enthalpy
of
sublimaGon,
Hsub
is
the
molar
enthalpy
change
when
a
substance
sublimes
(s
g).
Hsub
=
Hm(vapor)
Hm(solid)
Enthalpy,
H
is
a
state
function
Value
for
enthalpy
is
the
same
if
it
occurs
in
one
step
or
multiple
steps
Hsub
=
Hfus
+
Hvap
Figure 7.24
54
The
Enthalpy
of
Physical
Change
(7.11)
VaporizaFon,
fusion,
and
sublimaFon
all
have
reverse
processes.
- VaporizaFon:
liquid
gas
Endothermic
process,
Hvap
(+)
- CondensaFon:
gas
liquid
- Fusion:
solid
liquid
- Freezing:
liquid
solid
Endothermic
process,
Hfus
(+)
- SublimaFon:
solid
gas
- DeposiFon:
gas
solid
Endothermic
process,
Hsub
(+)
55
The
Enthalpy
of
Physical
Change
(7.11)
The
enthalpy
change
for
a
reverse
process
has
the
same
value
but
the
opposite
sign
of
the
enthalpy
change
for
the
forward
process
(at
the
same
temperature).
Hreverse
process
=
-
Hforward
process
Vaporization
(liquid
gas)
process
is
endothermic,
Hvap
(+)
Condensation
(gas
liquid)
is
the
reverse
process
of
vaporization.
Hcon
=
-
Hvap
Hcon
is
exothermic
(-)
56
The
Enthalpy
of
Physical
Change
(7.11)
SecFon
summary:
The
enthalpy
change
for
a
reverse
reacOon
is
the
negaOve
of
the
enthalpy
change
for
the
forward
reacOon.
Because
it
is
a
state
funcOon,
enthalpy
changes
can
be
added
to
obtain
the
value
for
an
overall
process.
57
Hea;ng
Curves
(7.12)
A
heaGng
curve
is
a
graph
showing
the
variaFon
in
the
temperature
of
a
sample
as
it
is
heated
at
constant
rate
and
constant
pressure.
58
Hea;ng
Curves
(7.12)
H2O
Heating/
cooling
Endothermic
Phase
Change
heating/cooling
Exothermic
Phase
Change
heating/cooling
(J)
59
Figure 7.26
Hea;ng
Curves
(7.12)
H2O
Heating
/cooling
Endothermic
Phase
Change
For phase changes: q = mol(H phase change )
heating/cooling
Phase
Change
heating/cooling
For heating/cooling changes:
q = (mass)(Cs )(T ) or
q = (mol)(CP,m )(T )
Exothermic
(J)
60
Figure 7.26
Hea;ng
Curves
(7.12)
Example:
How
many
joules
of
energy
must
be
absorbed
by
5.00
x
102
g
of
H2O
at
50.0oC
to
convert
it
to
steam
at
120oC?
(Hvap
for
water
=
40.7
kJ/
mol,
CP,m
(water)
75.3
J/mol
oC,
CP,m
(steam)
=
36.4
J/mol
oC)
50C(liquid)
100C(liquid)
100C(vapor)
120C(vapor)
1) 50C(liquid)
100C(liquid)
q = (mols)(CP,m(water ) )(T )
! 5.00x10 2 g H 2O $! 1mol H 2O $
& = 27.75mol H 2O
#
&#
18.02g
H
O
"
%"
%
2
q = (27.75mol)(75.3J / molC)(100.0C 50.0C) = 104500J
2) 100C(liquid)
100C(vapor)
q = (mols)(H vap )
104500J +1129000J + 20200J = 1.25x10 6 J
q = (27.75mol)(40.7kJ / mol) = 1129kJ
3) 100C(vapor)
120C(vapor)
q = (mols)(CP,m(steam) )(T )
q = (27.75mol)(36.4J / molC)(120.0C 100.0C) = 20200J
61
Hea;ng
Curves
(7.12)
SecFon
summary:
The
temperature
of
a
sample
is
constant
at
its
melOng
and
boiling
points,
even
though
heat
is
being
supplied.
The
slope
of
a
heaOng
curve
is
steeper
for
a
phase
with
a
low
heat
capacity
than
for
one
with
a
high
heat
capacity.
62
Reac;on
Enthalpies
(7.13)
A
thermochemial
equaGon
consists
of
a
chemical
equaFon
together
with
a
statement
of
the
corresponding
enthalpy
change.
The
enthalpy
change
for
a
reacFon
is
called
the
enthalpy
of
reacGon,
Hrxn.
C6 H12O6 (l) + 6 O2 (g) 6 CO2 (g) + 6 H 2O(l) + 3523 kJ
Heat
is
a
product
then
exothermic
Heat
is
a
reactant
then
endothermic
63
Reac;on
Enthalpies
(7.13)
The
stoichiometric
coecients
in
thermochemical
equaFons
must
be
interpreted
as
mols
of
reactants
and
products.
Example
below:
One
mole
of
C6H12O6
reacts
with
six
moles
of
O2
to
produce
six
moles
of
CO2
and
six
moles
of
H2O.
C6 H12O6 (l) + 6 O2 (g) 6 CO2 (g) + 6 H 2O(l) + 3523 kJ
64
Reac;on
Enthalpies
(7.13)
Thermochemical
reacFons
should
always
be
interpreted
as
the
enthalpy
change
for
the
reacFon
exactly
as
it
is
wriOen.
This
specic
amount
of
reacFon
is
one
mole
of
reacGon
(mol
rxn).
This
is
where
the
units
kJ/mol
or
J/
mol
originate.
C6 H12O6 (l) + 6 O2 (g) 6 CO2 (g) + 6 H 2O(l) + 3523 kJ
! 1mol rxn $ ! 3523kJ $
#
& or #
&
" 3523kJ % " 1mol rxn %
65
Reac;on
Enthalpies
(7.13)
The
enthalpy
change
for
a
reverse
reacFon
has
the
same
value
but
an
opposite
sign
as
that
of
the
forward
reacFon.
C6 H12O6 (l) + 6 O2 (g) 6 CO2 (g) + 6 H 2O(l) + 3523 kJ
3523 kJ + 6 CO2 (g) + 6 H 2O(l) C6 H12O6 (l) + 6 O2 (g)
For
the
reverse
reaction,
change
the
sign
of
Hrxn.
66
Reac;on
Enthalpies
(7.13)
Example:
What
is
the
change
in
enthalpy
when
425
g
of
C6H12O6
is
burned
in
the
presence
of
excess
oxygen
gas?
C6 H12O6 (l) + 6 O2 (g) 6 CO2 (g) + 6 H 2O(l) + 3523 kJ
Find
moles
of
C6H12O6
Find
moles
of
reaction
Find
enthalpy
change
! 425g C6 H12O6 $! 1mol C6 H12O6 $! 1mol rxn $! 3523kJ $
&#
&#
#
&#
& = 8310kJ
"
%" 180.18g C6 H12O6 %" 1mol C6 H12O6 %" 1mol rxn %
67
Reac;on
Enthalpies
(7.13)
SecFon
summary:
A
thermochemical
equaOon
is
a
statement
of
a
chemical
equaOon
and
the
corresponding
reacOon
enthalpy,
the
enthalpy
change
for
the
stoichiometric
amounts
of
substances
in
the
chemical
equaOon.
68
Standard
Reac;on
Enthalpies
(7.15)
The
enthalpy
change
for
a
reacFon
depends
on
the
physical
states
of
the
products
and
reactants.
CH4(g)
+
2O2(g)
CO2(g)
+
2H2O(g)
+
802
kJ
CH4(g)
+
2O2(g)
CO2(g)
+
2H2O(l)
+
890.
kJ
Enthalpy
of
a
reacFon
depends
on:
Phases
of
the
reactants
and
products
CondiFons
of
reactants
and
products
(example
pressure)
69
Standard
Reac;on
Enthalpies
(7.15)
The
standard
state
for
a
substance
is
its
pure
form
at
exactly
1
bar
of
pressure.
Examples:
Sodium:
Na(s)
Oxygen:
O2(g)
Iron:
Fe(s)
70
Standard
Reac;on
Enthalpies
(7.15)
Enthalpy
of
reacFon
also
depends
on
the
condiFons
at
which
the
measurement
was
taken.
Most
texts
and
tables
give
data
for
reacFons
in
which
each
product
and
reactant
is
in
its
standard
state.
Most
thermochemical
data
are
reported
for
25oC
(298.15
K).
Temperature
is
NOT
part
of
the
deniGon
of
standard
state.
This
is
just
the
most
common
temperature
used
in
collecFng
data.
71
Standard
Reac;on
Enthalpies
(7.15)
The
standard
reacGon
enthalpy
(Ho)
is
the
reacFon
enthalpy
when
reactants
and
products
are
in
their
standard
states.
Represented
by
Ho
instead
of
H
72
Standard
Reac;on
Enthalpies
(7.15)
SecFon
summary:
Standard
reacOon
enthalpies
refer
to
reacOons
in
which
the
reactants
and
products
are
in
their
standard
state,
the
pure
form
at
1
bar.
They
are
usually
reported
for
a
temperature
of
298.15
K.
73
Hesss
Law
(7.16)
Hesss
law
states
that
the
overall
reacFon
enthalpy
is
the
sum
of
the
reacFon
enthalpies
of
the
steps
into
which
the
reacFon
can
be
divided.
Hrxn
=
Hrxn
Figure 7.30
74
Hesss
Law
(7.16)
Whatever
you
do
to
the
rxn,
do
the
same
to
its
H.
If
you
reverse
a
reacFon,
change
the
sign
on
H.
If
you
have
to
mulFply
the
coecients
in
a
reacFon
by
a
given
integer,
mulFply
H
by
the
same
integer.
When
you
add
reacFons,
add
their
H.
75
Hesss
Law
(7.16)
Example:
Use
the
informaFon
below
to
calculate
Ho
for
the
reacFon:
4 FeO(s) + O 2(g) 2 Fe 2O 3(s)
2 Fe(s) + O 2(g) 2 FeO(s)
4 Fe(s) + 3 O 2(g) 2 Fe 2 O3(s)
4FeO(s) 4 Fe(s) + 2 O 2(g)
4 Fe(s) + 3 O 2(g) 2 Fe 2 O3(s)
H o = 544 kJ
H o = 1648 kJ
H o = 2(544 kJ) = +1088kJ
H o = 1648 kJ
4 FeO(s) + 4 Fe(s) + 3 O 2(g) 4 Fe(s) + 2 O 2(g) + 2 Fe 2 O3(s) H o = 560 kJ
4 FeO(s) + O 2(g) 2 Fe 2 O3(s)
H o = 560 kJ
76
Hesss
Law
(7.16)
SecFon
summary:
According
to
Hesss
law,
thermochemical
equaOons
for
the
individual
steps
of
a
reacOon
sequence
may
be
combined
to
give
the
thermochemical
equaOon
for
the
overall
reacOon.
77
Standard
Enthalpies
of
Forma;on
(7.18)
The
standard
molar
enthalpy
of
formaGon
(Hfo)
of
a
substance
is
the
enthalpy
change
for
the
reacFon
in
which
one
mole
of
the
substance
(in
a
specied
state)
is
formed
from
its
elements
in
their
most
stable
forms.
Only
one
mole
of
product
can
form
Fractional
coefBicients
for
reactants
can
be
used.
78
Standard
Enthalpies
of
Forma;on
(7.18)
Example:
The
standard
molar
enthalpy
of
formaFon
for
phosphoric
acid
in
the
solid
state
is
-1281
kJ/mol.
Phosphorous
in
its
standard
state
is
P4(s).
Write
the
equaFon
that
corresponds
to
the
enthalpy
of
formaFon
for
phosphoric
acid.
Phosphoric
acid
-
H3PO4(s)
H 2(g) + P4(s) + O 2(g) H 3PO 4(s) + 1281 kJ
Balance
the
reaction
3
1
H 2(g) + P4(s) + 2O 2(g) H 3PO 4(s) + 1281 kJ
2
4
79
Standard
Enthalpies
of
Forma;on
(7.18)
Standard
enthalpies
of
formaFon
can
be
used
to
calculate
enthalpies
of
reacFon.
o
rxn
= n H
n
o
f products
n H
o
f reactants
n = stoichiometric coefficients
80
Standard
Enthalpies
of
Forma;on
(7.18)
Example:
Calculate
the
Ho298
for
the
following
reacFon
from
data
below.
H f C3H8 = 103.8kJ / mol
H f H2O (l ) = 285.8kJ / mol
H f CO2 = 395.3kJ / mol
H f O2 = 0.0kJ / mol
C3 H 8 (g) + 5O2 (g) 3CO2 (g) + 4H 2O(l)
H rxn = [3mol(H f CO2 ) + 4mol(H f H2O ( l ) )][1mol(H f C3H8 ) + 5mol(H f O2 )]
H rxn = [3mol(395.3kJ / mol) + 4mol(285.8kJ / mol)]
[1mol(103.8kJ / mol) + 5mol(0.0kJ / mol)]
H rxn = [2329.1kJ][103.8kJ] = 2225.3kJ
81
Standard
Enthalpies
of
Forma;on
(7.18)
SecFon
summary:
Standard
enthalpies
of
formaOon
can
be
combined
to
obtain
the
standard
enthalpy
of
any
reacOon.
82
Bond
Enthalpies
(7.20)
In
a
chemical
reacFon,
bond
breaking
is
always
endothermic
and
bond
formaOon
is
always
exothermic.
The
strength
of
a
chemical
bond
is
the
bond
enthalpy
(HB).
We
can
esFmate
reacFon
enthalpies
if
we
know
the
enthalpy
changes
that
accompany
the
breaking
and
making
of
bonds.
83
Bond
Enthalpies
(7.20)
Bond
breaking
is
always
endothermic.
Bond
formaOon
is
always
exothermic.
Bond
energies
can
also
be
used
to
calculate
Horxn.
Horxn
=
HB
reactants
-
HB
products
Calculating
Hrxn
using
bond
energies:
reactants
products
Calculating
Hrxn
using
Hf
:
products
reactants
84
Bond
Enthalpies
(7.20)
Example:
EsFmate
the
enthalpy
of
reacFon
for
the
combusFon
of
methane
using
the
informaFon
in
Tables
7.7
and
7.8
Hrxn = [4(H B, C-H ) + 2(H B, O=O )][2(H B, C=O ) + 4(H B, H-O )]
Hrxn = [4(412kJ / mol) + 2(496kJ / mol)]
[2(743kJ / mol) + 4(463kJ / mol)]
Hrxn = [2640kJ / mol][3338kJ / mol)] = 698kJ / mol
85
Bond
Enthalpies
(7.20)
SecFon
summary:
Bond
enthalpies
can
be
used
to
calculate
enthalpies
of
reacOon.
Bond
breaking
is
endothermic.
Bond
formaOon
is
exothermic.
86