Chapter 11 - Thermochemistry
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Transcript Chapter 11 - Thermochemistry
Chapter 17 - Thermochemistry
Heat and Chemical Change
Energy and Heat
Thermochemistry
- concerned
with heat changes that occur
during chemical reactions.
2
Energy and Heat
Energy
- capacity for doing work
or supplying heat
• weightless, odorless, tasteless
• if within the chemical
substances - called chemical
potential energy
3
Energy and Heat
Gasoline
contains a significant
amount of chemical potential
energy
4
Energy and Heat
- represented by “q”, is
energy that transfers from one
object to another, because of a
temperature difference between
them.
• only changes can be detected!
• flows from warmer cooler
object
Heat
5
Exothermic and Endothermic
Processes
Essentially
all chemical
reactions, and changes in
physical state, involve either:
• release of heat, or
• absorption of heat
Exothermic and Endothermic
In
studying heat changes, think of
defining these two parts:
• the system - the part of the
universe on which you focus
your attention
• the surroundings - includes
everything else in the universe
Exothermic and Endothermic
Together,
the system and it’s
surroundings constitute the
universe
Thermochemistry is concerned
with the flow of heat from the
system to it’s surroundings, and
vice-versa.
• Figure 17.2, page 506
Law of Conservation of Energy
The
Law of Conservation of
Energy states that in any
chemical or physical process,
energy is neither created nor
destroyed.
• All the energy is accounted for
as work, stored energy, or heat.
Endothermic
Fig.
17.2a, p.506 - heat flowing
into a system from it’s
surroundings:
• defined as positive
• q has a positive value
• called endothermic
–system gains heat as the
surroundings cool down
Endothermic
Exothermic
Fig.
17.2b, p.506 - heat flowing out of
a system into it’s surroundings:
• defined as negative
• q has a negative value
• called exothermic
–system loses heat as the
surroundings heat up
Exothermic
Exothermic and Endothermic
Every
reaction has an energy
change associated with it
Exothermic reactions release
energy, usually in the form of heat.
Endothermic reactions absorb
energy
Energy is stored in bonds
between atoms
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Heat Capacity and Specific Heat
A calorie is defined as the
quantity of heat needed to
raise the temperature of 1 g of
pure water 1 oC.
15
Heat Capacity and Specific Heat
• Used except when referring
to food
• a Calorie, written with a
capital C, always refers to
the energy in food
• 1 Calorie = 1 kilocalorie =
1000 cal.
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Heat Capacity and Specific Heat
The
calorie is also related to
the joule, the SI unit of heat
and energy
• named after James Prescott
Joule
• 4.184 J = 1 cal
17
Heat Capacity and Specific Heat
Heat
Capacity - the amount
of heat needed to increase
the temperature of an object
exactly 1 oC
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Heat Capacity and Specific Heat
Specific
Heat Capacity - the
amount of heat it takes to raise the
temperature of 1 gram of the
substance by 1 oC
(abbreviated “C”)
• often called simply “Specific Heat”
• Note Table 17.1, page 508
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Heat Capacity and Specific Heat
Water has a HUGE value,
compared to other
chemicals
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Heat Capacity and Specific Heat
water, C = 4.18 J/(g oC), and
also C = 1.00 cal/(g oC)
Thus, for water:
• it takes a long time to heat up,
and
• it takes a long time to cool off!
Water is used as a coolant!
For
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Heat Capacity and Specific Heat
q = mass (g) x T x C
heat
abbreviated as “q”
T = change in temperature
C = Specific Heat
Units are either
J/(g oC) or cal/(g oC)
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Example
When 435J of heat is added to 3.4 g of
olive oil at 21 °C, the temperature
increases to 85 °C. What is the specific
heat of olive oil?
q = m x T x C
C= q
m x T
C=
C=
q
m x T
435J
3.4g x (85°C - 21°C)
C = 2 J/g°C
Calorimetry
Calorimetry
- the accurate and
precise measurement of heat
change for chemical and physical
processes.
The device used to measure the
absorption or release of heat in
chemical or physical processes is
called a Calorimeter
Calorimetry
Foam
cups are excellent heat
insulators, and are commonly
used as simple calorimeters
For
systems at constant pressure,
the heat content is the same as a
property called Enthalpy (H) of the
system.
Calorimeter
Calorimetry
in enthalpy = H
q = H These terms will be
used interchangeably in this
textbook.
Changes
Calorimetry
Thus,
q = H = m x C x T
H
is negative for an
exothermic reaction.
H
is positive for an
endothermic reaction.
Calorimetry
Calorimetry
experiments can
be performed at a constant
volume using a device called
a “bomb calorimeter” - a
closed system
Bomb Calorimeter
Calorimeter Problem
50ml of HCl
(in H2O)
Ti= 22.5°C
Calorimeter Problem
Add 50ml of NaOH
(in H2O)
Ti= 22.5°C
Calorimeter Problem
Chemical
Reaction
Calorimeter Problem
100ml of HCl and NaOH
(in H2O)
Tf= 26°C
Calorimeter Problem
1ml of H2O = 1g
100ml of H2O = 100g
m = 100g
Ti= 22.5°C
Tf= 26°C
CH20= 4.18J/g°C
Calorimeter Problem
H = m x C x T
H = m x C x (Tf –Ti)
= 100g x 4.18J/g°C x (26°C - 22.5°C)
H = 1460J = 1.46kJ
Energy
C + O2 CO2 + 395 kJ
C + O2
395kJ
C O2
Reactants
Products
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In terms of bonds
O
O
C
O
C
O
Breaking this bond will require energy.
O
C
O
O C O
Making these bonds gives you energy.
In this case making the bonds gives
you more energy than breaking them.
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Exothermic
The
products are lower in
energy than the reactants
Releases energy
40
Energy
CaCO
CaO
CaCO
CaO
+ CO+2 CO2
3 + 176
3 kJ
CaO + CO2
176 kJ
CaCO3
Reactants
Products
41
Endothermic
The
products are higher in
energy than the reactants
Absorbs energy
42
Chemistry Happens in
MOLES
An
equation that includes
energy is called a
thermochemical equation
CH4+2O2CO2+2H2O + 802.2 kJ
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CH4+2O2CO2+2H2O + 802.2kJ
1
mole of CH4 releases 802.2kJ
of energy.
When you make 802.2 kJ you
also make 2 moles of water.
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Thermochemical Equations
A heat
of reaction is the heat
change for the equation, exactly as
written
• The physical state of reactants
and products must also be given.
• Standard conditions for the
reaction is 101.3 kPa (1 atm.)
and 25 oC
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CH4+2O2 CO2 + 2 H2O + 802.2 kJ
If
10. 3 grams of CH4 are burned
completely, how much heat will be
produced?
10.3g CH4
1 mol CH4
802.2 kJ
16.05g CH4 1mol CH4
ΔH = 514 kJ
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CH4+2O2 CO2+2H2O + 802.2 kJ
How many liters of O2 at STP
would be required to produce 23
kJ of heat?
22.4L x 2 = 44.8L produces 802.2kJ
23kJ
= 0.029 0.029 x 44.8L =
802.2kJ
VO2 = 1.30 L
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CH4+2O2 CO2+2H2O+802.2 kJ
How
many grams of water would
be produced with 506 kJ of heat?
2 mol of H2O produced with 802.2kJ
2 mol of H2O is 36g
506kJ
x 36g =
802.2kJ
22.71g of H2O
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Heat of Combustion
The
heat from the reaction that
completely burns 1 mole of a
substance
Note Table 17.2 page 517
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Summary, so far...
Enthalpy
The
heat content a substance has at a
given temperature and pressure
Can’t be measured directly because
there is no set starting point
The reactants start with a heat content
The products end up with a heat
content
So we can measure how much
enthalpy changes
51
Enthalpy
Symbol
is H
Change in enthalpy is H (delta H)
If heat is released, the heat content of
the products is lower
H is negative (exothermic)
If heat is absorbed, the heat content
of the products is higher
H is positive (endothermic)
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Energy
Change is down
H is <0
Reactants
Products
53
Energy
Change is up
H is > 0
Reactants
Products
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Heat of Reaction
The
heat that is released or
absorbed in a chemical reaction
Equivalent to H
C + O2(g) CO2(g) + 393.5 kJ
C + O2(g) CO2(g)
H = -393.5 kJ
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Heat of Reaction
In thermochemical equation, it
is important to indicate the
physical state
H2(g) + 1/2O2 (g) H2O(g)
H = -241.8 kJ
H2(g) + 1/2O2 (g) H2O(l)
H = -285.8 kJ
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Section 17.3
Heat in Changes of State
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Heats of Fusion and
Solidification
Molar
Heat of Fusion (Hfus)
- the heat absorbed by one
mole of a substance in
melting from a solid to a
liquid
58
Heats of Fusion and
Solidification
Molar
Heat of Solidification
(Hsolid) - heat lost when one
mole of liquid solidifies
59
Heats of Fusion and
Solidification
Heat
absorbed by a melting solid
is equal to heat lost when a liquid
solidifies
• Thus, Hfus = -Hsolid
Note Table 17.3, page 522
Sample Problem 17-4, page 421
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Sample Problem
How many kJs of heat are required to
melt a 10.0g popsicle at 0°C? Assume
the popsicle has the same molar mass
and heat of fusion as water.
It takes 6.01kJ to melt 1 mol of ice.
There are 18g in 1 mol of ice.
10g
x 6.01kJ/mol = 3.34 kJ
18g/mol
Heats of Vaporization and
Condensation
When
liquids absorb heat at their
boiling points, they become
vapors.
Molar Heat of Vaporization (Hvap)
- the amount of heat necessary to
vaporize one mole of a given
liquid.
Table 17.3, page 521
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Heats of Vaporization and
Condensation
Condensation is the opposite
of vaporization.
Molar Heat of Condensation
(Hcond) - amount of heat
released when one mole of
vapor condenses
Hvap = - Hcond
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ΔHfusion
ΔHvaporization
Heats of Vaporization and
Condensation
The large values for Hvap and
Hcond are the reason hot vapors
such as steam is very
dangerous
• You can receive a scalding
burn from steam when the heat
of condensation is released!
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Heats of Vaporization and
Condensation
H20(l) H20(g) m = 63.7g of liquid
Hvap = ?
63.7g
x 40.7kJ/mol
18g/mol
= 144kJ
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Heat of Solution
Heat
changes can also occur when a
solute dissolves in a solvent.
Molar Heat of Solution (Hsoln) - heat
change caused by dissolution of one
mole of substance
Sodium hydroxide provides a good
example of an exothermic molar heat
of solution:
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NaOH(s)
H2O(l)
Na1+(aq) + OH1-(aq)
Hsoln = - 445.1 kJ/mol
The heat is released as the ions
separate and interact with water,
releasing 445.1 kJ of heat as
Hsoln thus becoming so hot it
steams!
Sample Problem 17-7, page 526
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Section 17.4
Calculating Heat Changes
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Hess’s Law
If
you add two or more
thermochemical equations to give a
final equation, then you can also
add the heats of reaction to give
the final heat of reaction.
Called Hess’s law of heat summation
Example shown on page 529 for
graphite and diamonds
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Diamond to Graphite
C(s,diamond)
C(s,graphite)
C(s,diamond) + O2 CO2 ΔH=-393.5kJ
C(s,graphite) + O2 CO2 ΔH=-395.4kJ
CO2 C(s,graphite) + O2 ΔH=395.45kJ
C(s,diamond) + O2 CO2 ΔH=-393.5kJ
CO2 C(s,graphite) + O2 ΔH=395.45kJ
+
C(s,diam) C(s,graph)
ΔH=-1.9kJ
Why Does It Work?
If
you turn an equation around,
you change the sign:
H2(g)+1/2 O2(g)H2O(g) H=-285.5 kJ
H2O(g)H2(g)+1/2 O2(g)H =+285.5 kJ
If
you multiply the equation by a
number, you multiply the heat by
that number:
2H2O(g)H2(g)+O2(g) H =+571.0 kJ
Why does it work?
You
make the products, so you
need their heats of formation
You “unmake” the products so
you have to subtract their heats.
How do you get good at this?
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Standard Heats of Formation
H for a reaction that
produces 1 mol of a compound
from its elements at standard
conditions
Standard conditions: 25°C and 1
atm.
The
Symbol
is ΔHf
0
75
Standard Heats of Formation
The
standard heat of
formation of an element = 0
This
includes the diatomics
O2 N2
Cl2 etc……
76
What good are they?
Table
17.4, page 530 has
standard heats of formation
The heat of a reaction can be
calculated by:
• subtracting the heats of
formation of the reactants
from the products
Ho = (H 0f Products) - (H 0f Reactants)
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CH4(g) + 2 O2(g) CO2(g) + 2 H2O(g)
0
H f CH4 (g) = - 74.86 kJ/mol
0
H f O2(g) = 0 kJ/mol
0 CO (g) = - 393.5 kJ/mol
H f
2
0 H2O(g) = - 241.8 kJ/mol
H f
H= [-393.5+2(-241.8)]-[-74.68+2 (0)]
H= - 802.4 kJ
78
Examples
Sample
Problem 17-8, page 531
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