Chapter6 Energy and Chemical Reactions

Chemistry: The Molecular Science
Moore, Stanitski and Jurs
Chapter 6: Energy and Chemical Reactions
© 2008 Brooks/Cole 1
The Nature of Energy
Energy (E) = the capacity to do work.
Work (w) occurs when an object moves against a

resisting force:
w = −(resisting force) x (distance traveled)
w = −F d
All energy is either Kinetic or Potential energy.
The Nature of Energy
Kinetic energy (Ek) - Energy of motion
 macroscale = mechanical energy
 random nanoscale = thermal energy
 periodic nanoscale = acoustic energy
Ek = ½mv2 (m = mass, v = velocity of object)
Potential energy (Ep) – Energy of position. Stored E.

It may arise from:
 gravity: Ep = m g h (mass x gravity x height).
 charges held apart.
 bond energy.
Energy Units
joule (J) - SI unit (1 J = 1 kg m2s-2)
2.0 kg mass moving at 1.0 m/s (~2 mph):
Ek = ½ mv2 = ½ (2.0 kg)(1.0 m/s)2

= 1.0 kg m2 s-2
= 1.0 J
1 J is a relatively small amount of energy.

1 kJ (1000 J) is more common in chemical problems.
Energy Units
calorie (cal)
Originally:
“The energy needed to heat of 1g of water from 14.5
to 15.5 °C.”
Now: 1 cal = 4.184 J (exactly)
Dietary Calorie (Cal) - the “big C” calorie

Used on food products. 1 Cal = 1000 cal
= 1 kcal
Conservation of Energy
“Energy can neither be created nor destroyed”
E can only change form.
Total E of the universe is constant.
Also called the 1st Law of Thermodynamics
Conservation of Energy
A diver:
• Has Ep due to macroscale position.
• Converts Ep to macroscale Ek.
• Converts Ek,macroscale to Ek,nanoscale (motion of water, heat)
Energy and Working
If an object moves against a force, work is done.
• Lift a book
 you do work against gravity. The book’s Ep increases.
• Drop the book:

 Ep converts into Ek
 The book does work pushing the air aside.
• The book hits the floor

 no work is done on the floor (it does not move).
 Ek converts to a sound wave and T of the book and floor
increase (Ek converts to heat).
Energy and Working
In a chemical process, work occurs whenever
something expands or contracts.
Expansion pushes back the surrounding air.
Imagine the gas inside a balloon

 heat the gas.
 the gas expands and the balloon grows.
 the gas does work pushing back the rubber and
the air outside it.
Energy, Temperature and Heating
Temperature is a measure of the
thermal energy of a sample.
Thermal energy
• E of motion of atoms, molecules, and ions.
• Atoms of all materials are always in motion.
• Higher T = faster motion.
Consider a thermometer. As T increases:

 Atoms move faster, and on average get farther apart.
 V of the material increases.
 Length of liquid column increases.
Heat
• Thermal E transfer caused by a T difference.
• Heat flows from hotter to cooler objects until
they reach thermal equilibrium (have equal T ).
Systems, Surroundings & Internal Energy
System = the part of the universe under study
 chemicals in a flask.
 the coffee in your coffee cup.
 my textbook.
Surroundings = rest of the universe (or as much as
needed…)
 the flask.
 perhaps the flask and this classroom.
 perhaps the flask and all of the building, etc.
Universe = System + Surroundings
Internal energy = E within the system because of
nanoscale position or motion
Einternal= sum of all nanoscale Ek and Ep

 nanoscale Ek = thermal energy
 nanoscale Ep
• ion/ion attraction or repulsion
• nucleus/electron attraction
• proton/proton repulsion …..
Internal energy depends on
• Temperature
 higher T = larger Ek for the nanoscale particles.
• Type of material
 nanoscale Ek depends upon the particle mass.
 nanoscale Ep depends upon the type(s) of particle.
• Amount of material
 number of particles.
 double sample size, double Einternal, etc.
Calculating Thermodynamic Changes
Energy change of system = final E – initial E
ΔE = Efinal – Einitial
A system can gain or lose E

SURROUNDINGS SURROUNDINGS
SYSTEM SYSTEM
Efinal Einitial
ΔE > 0 E in ΔE < 0 E out
Einitial Efinal
ΔE positive: internal energy increases ΔE negative: internal energy decreases
Calculating Thermodynamic Changes
• No subscript? Refers to the system: E = Esystem
• E is transferred by heat or by work.
• Conservation of energy becomes: ΔE = q + w
heat work
SURROUNDINGS
SYSTEM
Heat transfer in Heat transfer out
q>0 q<0
ΔE = q + w
Work transfer in Work transfer out
w>0 w<0
Note the same sign convention for q and w
Heat Capacity
Heat capacity = E required to raise the T of an object
by 1°C. Varies from material to material.
Specific heat capacity (c)

• E needed to heat 1 g of substance by 1°C.
Molar heat capacity (cm)

• E needed to heat 1 mole of substance by 1°C.
Heat Capacity
E required to change the T of an object is:
Heat required = mass x specific heat x ΔT

q = m c ΔT
or…
Heat required = moles x molar heat capacity x ΔT

q = n cm ΔT
Substance c (J g-1 °C-1) cm (J mol-1 °C-1)
Elements
Al(s) 0.902 24.3
C (graphite) 0.720 8.65
Heat Fe(s) 0.451 25.1
Cu(s) 0.385 24.4
Capacities Au(s) 0.129 25.4
Compounds
NH3(l) 4.70 80.1
H2O(l) 4.184 75.3
C2H5OH(l) 2.46 112.
(CH2OH)2(l) 2.42 149.
H2O(s) 2.06 37.1
CCl4(l) 0.861 132.
CCl2F2(l) 0.598 72.3
Common solids
wood 1.76
concrete 0.88
glass 0.84
granite 0.79
Heat Capacity
Example
How much energy will be used to heat 500.0 g of iron
from 22°C to 55°C? cFe = 0.451 J g-1 °C-1.
Heat required = mass x specific heat x ΔT

q = m c ΔT
q = 500.0 g (0.451 J g-1 °C-1)(55−22)°C
q = 7442 J = +7.4 kJ
+ sign, E added to the system (the iron)
Heat Capacity
Example
24.1 kJ of energy is lost by a 250. g aluminum block.
If the block is initially at 125.0°C what will be its final
temperature? (cAl = 0.902 J g-1 °C-1)
q = m c ΔT
ΔT = q / (m c)
heat is lost, q is negative
ΔT = −24.1 x 103 J /(250. g x 0.902 J g-1 °C-1)
ΔT = Tfinal – Tinital = −107 °C
Thus Tfinal = ΔT + Tinital = −107 + 125°C = 18°C
Heat Capacity
A 200. g block of Cu at 500.°C is plunged into 1000. g of water
(T = 23.4 °C) in an insulated container. What will be the final
equilibrium T of water and Cu? (cCu = 0.385 J g-1 °C-1)
Cu cools (−q); water heats (+q); q = m c ΔT
Heat lost by Cu = −(200. g)(0.385 J g-1 °C-1)(Tfinal− 500)
Heat gained by H2O = +(1000. g)(4.184 J g-1 °C-1)(Tfinal− 23.4)
So: −77.0(Tfinal – 500) = 4184(Tfinal – 23.4)

(4184 + 77.0)Tfinal = 38500 + 97906
Tfinal = 32.0°C
(Note: Tfinal must be between Thot and Tcold)
Conservation of Energy and Changes of State
When heat is: Added to a system
 q is positive
 the change is endothermic
Removed from a system
 q is negative
 the change is exothermic.
Water Boils: H2O(l)  H2O(g) endothermic
Steam Condenses: H2O(g)  H2O(l) exothermic
Work occurs as the sample expands or contracts.

Overall: ΔE = q + w
A liquid cools from 45°C to 30°C, transferring 911 J to
the surroundings. No work is done on or by the
liquid. What is ΔEliquid?
ΔEliquid = qliquid + wliquid here wliquid = 0

Heat transfers from the liquid to the surroundings:
qliquid = -911 J (qsurroundings = +911 J)
ΔEliquid = -911J
A system does 50.2 J of work on its surroundings and
there is a simultaneous 90.1 J heat transfer from the
surroundings to the system. What is ΔEsystem?
Work done on the surroundings by the system

Heat transfers from the surroundings to the system
wsystem = -50.2 J qsystem = +90.1 J
ΔEsystem = qsystem + wsystem

ΔEsystem = -50.2 J +90.1 J = +39.9 J
Enthalpy: Heat Transfer at Constant P
Because ΔE = q + w:
 At Constant V: ΔE = qV
• subscript V shows fixed V
• work requires motion against an opposing force.
• constant V = no motion, so w = 0.
 At Constant P: ΔE = qP + watm= ΔH + watm

• Subscript P shows fixed P.
• watm = work done to push back the atmosphere
• H = enthalpy. ΔH = qp
Freezing and Melting (Fusion)
During freezing (or melting)
• Substance loses (or gains) E, but…
• T remains constant.
50
Example:
Temperature (°C)
25
Convert ice at Ice is melting. T

remains at 0°C
-50°C to water Water warms
from 0 to 50°C
0
at +50°C
-25
Ice warms from -50

to 0°C
-50
0 100 200 300 400 500 600

Quantity of energy transferred (J)
Changes of State
ΔHfusion = qP = heat to melt a solid.
Change Name value for H2O (J/g)

solid → liq enthalpy of fusion 333
liq → gas enthalpy of vaporization 2260
liq → solid enthalpy of freezing −333
gas → liq enthalpy of condensation −2260
Note: ΔHfusion = − ΔHfreezing etc.

qfusion = −qfreezing
State Functions and Path Independence
State functions State
Always have the same value whenever functions
the system is in the same state.
H E
P V
Two equal mass samples of water produced by:
T etc.
1. Heating one from 20°C to 50°C.
2. Cooling the other from 100°C to 50°C.
have identical final H (and V, P, E…).
State function changes are path independent.

ΔH = Hfinal – Hinitial is constant.
Thermochemical Expressions
ΔH = qP can be added to a balanced equation.
CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(g) ΔH° = −803.05 kJ

CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(l) ΔH° = −890.36 kJ
ΔH° is the standard enthalpy change

 P = 1 bar.
 T must be stated (if it isn’t, assume 25°C).
 ΔH° is a molar value. Burn 1 mol of CH4 with 2 mol O2 to
form 2 mol of liquid water and release 890 kJ of heat
 Change a physical state, change ΔH° : H2O(l) vs. H2O(g)
Enthalpy Changes for Chemical Reactions
Calculate the heat generated when 500. g of propane
burns in excess O2.
C3H8(l) + 5 O2(g) 3 CO2(g) + 4 H2O(l) ΔH° = – 2220. kJ
Molar mass of C3H8 = 44.097 g/mol.

nC3H8 = (500. g) / (44.097 g/mol)
= 11.34 mol C3H8
Since ΔH° = qp = –2220. kJ/(1 mol C3H8)
q = (11.34 mol C3H8) (–2220. kJ / mol C3H8 )
= –2.52 x 104 kJ
Where Does the Energy Come From?
Bond Enthalpy (bond energy)
• Equals the strength of 1 mole of bonds
• Always positive
 It takes E to break a bond
 Separated parts are less stable than the molecule.
 Less stable = higher E
• E is always released when a bond forms

 Product is more stable than the separated parts.
 More stable = lower E
Bond Enthalpies
During a chemical reaction:
Old bonds break: requires E (endothermic)
New bonds form: releases E (exothermic)
Both typically occur:
H2(g) + Cl2(g) 2 H(g) + 2 Cl(g) 2 HCl(g)
endothermic exothermic
ΔH= +678 kJ/mol ΔH= -862 kJ/mol
Bond Enthalpies
Overall, heat may be absorbed or released:
Exothermic reactions (ΔH < 0)

 E is released.
less stability
energy
 New bonds are more stable than the old, reactants
or products
 More bonds are formed than broken.
Endothermic reactions (ΔH > 0)

 E is absorbed.
less stability
energy
 New bonds are less stable than the old, products
or reactants
 Fewer bonds are formed than broken

Measuring Enthalpy Changes
Heat transfers are measured with a calorimeter.
Common types:
• Bomb calorimeter.
 rigid steel container.
 filled with O2(g) and a small sample to be burnt.
 constant V, so qV = ΔE
• Flame calorimeter.
 samples burnt in an open flame.
 constant P, so qp = ΔH
• Coffee-cup calorimeter in lab (constant P).

Bomb Calorimeter
Measure ΔT of the water. Constant V: qV = ΔE
Conservation of E:
qreaction + qbomb + qwater = 0
or
−qreaction = qbomb + qwater
with
qbomb = mcalccalΔT = CcalΔT
A constant for a calorimeter
Octane (0.600 g) was burned in a bomb calorimeter containing
751 g of water. T increased from 22.15°C to 29.12°C. Calculate
the heat evolved per mole of octane burned. Ccal = 895 J°C-1.
2 C8H18(l) + 25 O2(g) 16 CO2(g) + 18 H2O(l)
−qreaction = qbomb + qwater
qbomb = CcalΔT = 895 J°C-1 (29.12 – 22.15)°C = +6238 J
qwater = m c ΔT = 751 g (4.184 J g-1 °C-1)(29.12 – 22.15)°C

= +2.190 x 104 J
So −qreaction = +6238 + 2.190 x 104 J = 2.81 x 104 J = 28.1 kJ

qreaction = −28.1 kJ
Octane (0.600 g) was burned in a bomb calorimeter… Calculate the heat
evolved per mole of octane burned
Molar mass of C8H18 = 114.23 g/mol.

nC8H18 = (0.600 g) / (114.23 g/mol)
= 0.00525 mol C8H18
Heat evolved /mol octane = −28.1 kJ

0.00525 mol
= −5.35 x 103 kJ/mol

= −5.35 MJ/mol
Coffee-cup calorimeter
Nested styrofoam cups prevent heat transfer
with the surroundings.
Constant P. ΔT measured.
q = qp = ΔH
Assume the cups do not absorb heat.

(Ccal = 0 and qcal = 0)
0.800g of Mg was added to 250. mL of 0.40 M HCl in
a coffee-cup calorimeter at 1 bar. Tsolution increased
from 23.4 to 37.9°C. Assume csolution = 4.184 J g-1°C-1
and complete the equation:
Mg(s) + 2 HCl(aq) H2(g) + MgCl2(aq) ΔH = ?
nMg = 0.800 g 1 mol = 0.03291 mol

24.31 g
nHCl = 0.250 L 0.4 mol = 0.100 mol

1L
1Mg ≡ 2HCl Mg is limiting

… 0.800g of Mg was added to 250. mL of 0.40 M HCl. T increased from 23.4 to
37.9°C. Assume the solution has c = 4.184 J g-1°C-1. ΔH = ?
qsolution = msolution c ΔT (msolution = macid + mMg )

= 250.8 g (4.184 J g-1 °C-1)(37.9 − 23.4)°C
= 15,220 J
Heat from the reaction went into the solution. So:
qsolution = – qreaction
qreaction = –15.22 kJ = ΔH
So ΔH = –15.22 kJ or ΔH = – 462 kJ
1 mol Mg 0.03291mol
exothermic
Hess’s Law
“If the equation for a reaction is the sum of the
equations for two or more other reactions, then ΔH°
for the 1st reaction must be the sum of the ΔH°
values of the other reactions.”
Another version:
“ΔH° for a reaction is the same whether it takes place
in a single step or several steps.”
H is a state function
Hess’s Law
Multiply a reaction, multiply ΔH.
Reverse a reaction, change the sign of ΔH.
2 CO(g) + O2(g) → 2 CO2 (g) ΔH = −566.0 kJ
Then
2 CO2(g) → 2 CO(g) + O2(g) ΔH = –1(–566.0 kJ)
= + 566.0 kJ
4 CO2(g) → 4 CO(g) + 2 O2(g) ΔH = –2(–566.0 kJ)

= +1132.0 kJ
Hess’s Law
Use Hess’s Law to find ΔH for unmeasured reactions.
Example
It is difficult to measure ΔH for:
2 C(graphite) + O2(g) 2 CO(g)
Some CO2 always forms. Calculate ΔH given:
C(graphite) + O2(g) CO2(g) ΔH = −393.5 kJ

2 CO(g) + O2(g) 2 CO2(g) ΔH = −566.0 kJ
Hess’s Law
Calculate ΔH for the reaction: 2C(graphite) + O2(g) → 2CO(g)
Rearrange:
+2[C + O2 CO2] +2(−393.5) = −787.0
−1[2 CO + O2 2 CO2] −1(−566.0) = +566.0
or:
2 C + 2 O2 2 CO2 ΔH° = −787.0 kJ
2 CO2 2 CO + O2 ΔH° = +566.0 kJ
Add, then cancel:
2 C + 2 O2 + 2 CO2 2 CO2 + 2 CO + O2 −221.0
2 C + O2 2 CO ΔH° = −221.0 kJ
Hess’s Law
Determine ΔH° for the production of coal gas:

2 C(s) + 2 H2O(g) CH4(g) + CO2(g)
Using:
C(s) + H2O(g) CO(g) + H2(g) ΔH° = 131.3 kJ A
CO(g) + H2O(g) CO2(g) + H2(g) ΔH° = −41.2 kJ B
CH4(g) + H2O(g) CO(g) + 3 H2(g) ΔH° = 206.1 kJ C
Hess’s Law
Want: 2 C(s) + 2 H2O(g) CH4(g) + CO2(g)
2 C on left, use 2 x A
2 C(s) + 2 H2O(g) 2 CO(g) + 2 H2(g) +262.6
1 CH4 on right, use −1 x C
CO(g) + 3 H2(g) CH4(g) + H2O(g) −206.1
1 CO2 on right, so use 1 x B
CO(g) + H2O(g) CO2(g) + H2(g) −41.2
Add and cancel:

2C + 3H2O + 2CO + 3H2 2CO + 3H2 + CH4 + H2O + CO2
15.3 kJ
change to 2 H2O 2 C + 2 H2O → CH4 + CO2 ΔH = 15.3 kJ
Standard Molar Enthalpy of Formation
Hess’s law problems often use a combustion or …
Formation reaction
Make 1 mol of compound from its elements in their
standard states.
H2 combustion:
2 H2(g) + O2(g) 2 H2O(l) ΔH° = −571.66 kJ
but the formation reaction is:
H2(g) + ½ O2(g) 1 H2O(l) ΔHf° = −285.83 kJ
f = formation
Standard Molar Enthalpy of Formation
Standard state = most stable form of the pure

element at P = 1 bar.
 e.g. C standard state = graphite (not diamond)
ΔHf° for any element in its standard state is zero.

(take 1 mol of the element and make… 1 mol of element)
ΔHf° (Br2(l) ) = 0 at 298 K

ΔHf° (Br2(g) ) ≠ 0 at 298 K
Standard Enthalpy of Formation (25°C)
Formula Name DHf°, kJ/mol
Appendix J Al2O3(s) aluminum oxide −1675.7
CaO(s) calcium oxide −635.09
CH4(g) methane −74.81
Notes C2H2(g) acetylene +226.73
• Most are negative C2H4(g) ethylene +52.26
(formation releases E), C2H6(g) ethane −84.68
but can be positive. C2H5OH(l) ethanol −277.69
H2O(g) water vapor −241.818
• If the physical state H2O(l) liquid water −285.830
changes, ΔHf° changes. NaF(s) sodium fluoride −573.647
NaCl(s) sodium chloride −411.153
SO2(g) sulfur dioxide −296.830
SO3(g) sulfur trioxide −395.72
Standard Molar Enthalpies of Formation
ΔH° ={(nproducts)(ΔHf° products)}
– {(nreactants)(ΔHf° reactants)}
Example
Calculate ΔH° for:
CH4(g) + NH3(g)  HCN(g) + 3 H2(g)
ΔH° = [1ΔHf°(HCN) + 3ΔHf°(H2)] −

[1ΔHf°(NH3) + 1ΔHf°(CH4)]
= [+134 + 3(0)] − [− 46.11 + (−74.85)] = 255 kJ/mol

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Chapter6 Energy and Chemical Reactions

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Chemistry: The Molecular Science

Moore, Stanitski and Jurs

Chapter 6: Energy and Chemical Reactions

Work (w) occurs when an object moves against a

All energy is either Kinetic or Potential energy.

Potential energy (Ep) – Energy of position. Stored E.

2.0 kg mass moving at 1.0 m/s (~2 mph):

Ek = ½ mv2 = ½ (2.0 kg)(1.0 m/s)2

1 J is a relatively small amount of energy.

Now: 1 cal = 4.184 J (exactly)

Dietary Calorie (Cal) - the “big C” calorie

E can only change form.

Total E of the universe is constant.

Also called the 1st Law of Thermodynamics

• Drop the book:

• The book hits the floor

Expansion pushes back the surrounding air.

Imagine the gas inside a balloon

Consider a thermometer. As T increases:

Universe = System + Surroundings

Einternal= sum of all nanoscale Ek and Ep

A system can gain or lose E

ΔE > 0 E in ΔE < 0 E out

ΔE positive: internal energy increases ΔE negative: internal energy decreases

Note the same sign convention for q and w

Specific heat capacity (c)

Molar heat capacity (cm)

Heat required = mass x specific heat x ΔT

Heat required = moles x molar heat capacity x ΔT

Heat required = mass x specific heat x ΔT

+ sign, E added to the system (the iron)

Cu cools (−q); water heats (+q); q = m c ΔT

Heat lost by Cu = −(200. g)(0.385 J g-1 °C-1)(Tfinal− 500)

Heat gained by H2O = +(1000. g)(4.184 J g-1 °C-1)(Tfinal− 23.4)

So: −77.0(Tfinal – 500) = 4184(Tfinal – 23.4)

Water Boils: H2O(l)  H2O(g) endothermic

Steam Condenses: H2O(g)  H2O(l) exothermic

Work occurs as the sample expands or contracts.

ΔEliquid = qliquid + wliquid here wliquid = 0

Work done on the surroundings by the system

ΔEsystem = qsystem + wsystem

 At Constant P: ΔE = qP + watm= ΔH + watm

Convert ice at Ice is melting. T

Ice warms from -50

0 100 200 300 400 500 600

Change Name value for H2O (J/g)

Note: ΔHfusion = − ΔHfreezing etc.

State function changes are path independent.

CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(g) ΔH° = −803.05 kJ

ΔH° is the standard enthalpy change

Molar mass of C3H8 = 44.097 g/mol.

• E is always released when a bond forms

Both typically occur:

H2(g) + Cl2(g) 2 H(g) + 2 Cl(g) 2 HCl(g)

Exothermic reactions (ΔH < 0)

 More bonds are formed than broken.

Endothermic reactions (ΔH > 0)

 Fewer bonds are formed than broken

• Coffee-cup calorimeter in lab (constant P).