First Law of

Thermodynamics

Thermochemistry
Enthalpies of
Enthalpy
Reaction

Hess’s Law

Foods and Fuels

Enthalpies of
Formation
 History of thermodynamics
 Study of energy and its
transformations
 Study began during industrial
revolution to develop relationships
among heat, work, and fuel in
steam engines.
 Examines relationships between
chemical reactions and energy
changes that involve heat.
Nature of Energy (definitions galore!)

 Define energy.

 Define work.

 Define heat.
Kinetic vs. Potential Energy
 Objects possess kinetic energy. How
can we represent kinetic energy in
an equation?

 How does potential energy differ

from kinetic energy?

 How is potential energy converted

to kinetic energy?
 Potential Energy under the
microscope

 Gravitational forces play little to no role in

interactions between atoms and
molecules. Predict what plays a much
more important role.

 **electrostatic potential energy**

 This energy is proportional to electrical charges
on two interacting objects, Q1 and Q2, and
inversely proportional to the distance, d.
Predict an equation.
 
Electrostatic Potential Energy (Eel)

Eel = κQ1Q2 / d

κ is a constant of
proportionality: 8.99 x 109 J-m/C2
 How can we make electrostatic potential
energy absolute zero?
 
At finite
separation
distances for
two charged
particles, Eel is
positive for like
charges and
negative for
opposite
charges. 
Think about it…

 If a cyclist is at the top of the hill

(not moving) and stops at the
bottom of the hill, are the potential
energies and kinetic energies the
same at both locations?
 Why?
 Units of Energy
 SI unit for energy is the joule (J) (more
often than not, use kJ)
 Using the kinetic energy equation, determine
what 1 J of units would be.

 Energy changes associated with

chemical reactions often expressed as
calories (cal)
 Originally defined as: amount of energy require
to raise the temperature of 1 g of water from
14.5 C to 15.5 C.
 1 cal = 4.184 J (exactly)
 Cal does not = cal.
 Which is the system, which is the
surroundings?

Open system:
matter and energy
can be exchanged
with surroundings
(ie: boiling water)

Closed System: can

exchange energy but not
matter with surroundings
(ie          

Isolated System: no
exchange of matter or
energy. (ie: coffee
thermos)
 Transferring Energy: Work and
Heat

 Define Force.

 How can we represent work in an

equation?
Example Problem

 A bowler lifts a 5.4 kg (12 lb)

bowling ball from ground level to a
height of 1.6 m (5.2 ft) and then
drops it.
 What happens to the potential energy
of the ball as it is raised?
 What is the quantity of work, in J, used
to raise the ball?
 After the ball is dropped, it gains
kinetic energy. If all the work done in
part b has been conver
November 29th, 2012

DO NOW:
 How are potential energy and
kinetic energy related?
 What is the kinetic energy, in J, of
the following:
 An Ar Atom moving at a speed of 650
m/s
 A mole of Ar atoms moving at 650
m/s?
 THE FIRST LAW OF
THERMODYNAMICS

 Energy can neither be created nor

destroyed
 Any energy lost by a system must be
gained by the surroundings (vice
versa)

 Energy is conserved
Internal energy

 How do we define internal energy?

 Chemistry is mainly concerned with

the change in energy in a system

 How do we represent the change in

energy in a system?
 Change in Energy

 Change in internal energy is denoted:

∆E = Efinal – Einital

 Generally we can not determine Efinal

– Einital for a practical system, but we
only need the ∆E to apply the law.

 Compare and contrast positive and

negative values of ∆E. What does the
sign change mean?
 Example

 For the reaction:

2 H2(g) + O2(g)  2 H2O(l)
 Which is the initial state and which is
final? Label them on the equation.

 As water is created, is energy lost or

gained to the surroundings?

 Does this indicate a positive ∆E or a

negative ∆E?
 Lets tie it together a little bit.

 How may a
system
exchange
energy with
its
surroundings?
Using the previous slide…

 How can we algebraically represent

a change in internal energy?
∆E = q + w
 As work is done on a system from its
surroundings, w > 0.
 As heat is gained in the system, q > 0.
Example Problem

Calculate the change in internal

energy for a process in which a
system absorbs 140 J of heat from
the surroundings and does 85 J of
work on the surroundings.
 Endothermic Vs. Exothermic
 Define Endothermic.

 Define Exothermic.

 Is the formation of H2 gas and O2

gas from H2O considered
endothermic or exothermic? Why?
 State Functions

 A state function is a property of a

system that is determined only by
the present state of the system, not
the path that system took.
 IE:
 Change in sea level
Vs.
Path Driven
 How does this relate to ∆E?
 ENTHALPY

 A system of a gas confined to a

container can be characterized by
several important properties. Which
properties are important?

 How are these properties similar to

∆E?

 Define Enthalpy.
Why is this equation useful?

 Since ∆E involves work, we must

consider the most commonly work
produced by chemical or physical
changes open to the atmosphere.
What is this type of work?

 Why is the equation or work we

gave yesterday no longer useful?
 Pressure – Volume Work

 Work involved in expansion or

compression of gas
 When pressure is constant:
 w = -P∆V

 If a system does not change its

volume during the course of a
process, does it do pressure-volume
work?
 Enthalpy Cont…

 When a change occurs at constant

pressure, how can we rewrite our
equation?

 When ∆H is positive, that means

the system has gained heat. That
means this is endothermic
 When ∆H is negative, that means
the system has lost heat. This
means it is exothermic.
 Practice, Practice, Practice!

 Complete the worksheet.

November 30th, 2012

Do Now:
 Indicate the sign of the enthalpy
change, ∆H, in these processes carried
out under atmospheric pressure and
indicate whether each process is
endothermic or exothermic:
 An ice cube melts
 1 g of butane is combusted in sufficient
oxygen to give complete combustion to
CO2 and H2O
Blah, Blah, Blah… so what did it all
mean!

 Enthalpy is ∆H= ∆E + P∆V

 MEANING: ∆H = (q + -P∆V) + P∆V
 So what does Enthalpy really tell
us?
 HEAT!
 So how is this different than ∆E?
 ∆E = change in heat at constant
volume
 ∆H = change in heat at constant P.
 The difference between the two is
Enthalpy of Reactions

∆H = Hfinal – Hinitial

 How could we re-write this

equation to represent ∆H for a
reaction?

 ∆H = Hproducts – Hreactants
Reactions

 When a numerical value is given for

∆Hrxn , a numerical value along with
the equation must be given.

 Suppose you are considering the

reaction seen at the beginning of
class, and that reaction has an
enthalpy of -848. How would we
write this correctly?
Thermochemical Reactions

 A thermochemical equation is a
balanced chemical equation that
shows the associated enthalpy
change but does not specify amount
of chemical involved.

 The coefficients in the balanced

equation represent the number of
moles of reactants and products
**IMPORTANT GUIDELINES**
 Enthalpy is EXTENSIVE.
 If 1 mol of CH4 is reacted with 2 moles of O2
and has an enthalpy of -890 J, how many J
would a reaction of 2 mol CH4 and 4 mol O2
give off?
 Enthalpy change for a rxn is equal in
magnitude, but opposite in sign, to ∆H
for the reverse reaction.
 The reverse rxn of the previously mentioned
rxn would have what value for ∆H?
 ∆H for a rxn depends on states of
reactants and products
 Practice

How much heat is released when 4.50

g of methane gas is burned in a
constant-pressure system? ( 1 mol
CH4 = -890 kJ)

Was this an endothermic or

exothermic process?
 Calorimetry

•The value of ∆H can be determined

experimentally by measuring heat
flow accompanying a reaction at
constant pressure.

•Measure of heat flow = calorimetry

•Determined by measure of
temperature change heat flow
produces
Temperature change

 Why does the temperature change

felt by certain objects/materials
differ?

 How does molar heat capacity differ

from specific heat capacity?
Specific Heat Capacity

 How might we solve for specific

heat capacity?

 Specific heat capacity values are

slightly different at different
temperatures. Temperature is
generally given.

 How can we rearrange our equation

to solve for q?
Practice!

 How much heat is needed to warm

250 g of water from 22 degrees
celcius to 98 degrees celcius? What
is the molar heat capacity of water?
December 5th, 2012
Do Now:

 How much heat is needed to warm

300 g of water from 20 degrees
celcius to 104 degrees celcius?
What is the molar heat capacity of
water?
 Coffee Cup Calorimetry

•Constant Pressure Calorimetry

•Why does the coffee cup act as a

constant pressure calorimeter?

•How do we measure the heat

change in a coffee cup
calorimeter?

•How does the q of the solution

relate to the q of the water
surrounding it?
 Example
 When a student mixes 50 mL of 1.0 M
HCl and 50 mL of 1.0M NaOH in a
coffee-cup calorimeter, the temperature
of the resultant solution increases from
21.0 C to 27.5 C. Calculate the enthalpy
change for the reaction in kJ/mol HCl,
assuming the calorimeter loses only a
negligible quantity of heat, that the total
volume of the solution is 100 mL, that
its density 1.0 g/mL, and specific heat is
4.18 J/gK
BOMB Calorimetry
 Bomb Calorimetry

 Constant-Volume Calorimetry
 Studies Combustion
 May only use after a standardization
measurement
 Once you have specific heat
capacity of calorimeter, you may
use:
qrxn = -Ccal X ∆T
 Difference between ∆E and ∆H is
very small
 Example
 The combustion of methylhydrazine
(CH6N2), a liquid rocket fuel, produces
N2(g), CO2 (g), and H2O (l).

When 4.00 g of methylhydrazine is

combusted in a bomb calorimeter, the
temperature of the calorimeter increases
from 25.00 C to 39.50 C. In a separate
experiment the heat capacity of the
calorimeter is measured to be 7.794 kJ/C.
Calculate the heat of reaction for the
combustion of a mole of CH6N2.
 Enthalpy of Formation

 How can we define Enthalpy of

Formation?
 An enthalpy of formation, Hf, is defined
as the enthalpy change for the reaction in
which a compound is made from its
constituent elements in their elemental
forms]

**BE AWARE: enthalpy of

formation values are generally
for 1 atom.
 Hess’s Law

 If a reaction is carried out in a

series of steps, ∆H for the overall
reaction equals the sum of the
enthalpy changes for the individual
steps.

 Example: Calculate the heat of

reaction at 1 atm and 298 K for the
following reaction:
 2HI (g) + F2  2HF (g) + I2 (2)
 PRACTICE

 Complete worksheet