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Chem 16

nd

Long Exam Reviewer

April 2015

THERMOCHEMISTRY
Thermodynamics study of heat and its
transformations to and from other forms of
energy
Thermochemistry

branch
of
thermodynamics that deals with the heat
involved with chemical and physical
changes
Fundamental premise When energy is
transferred from one object to another, it
appears as work and/or as heat.
System substances involved in the
chemical and physical changes under
investigation
Surroundings the environment around
the system
Universe system plus the surroundings
Energy capacity to do work
Work force acting through a distance
Kinetic Energy energy of motion
Potential Energy energy due to condition,
position, or composition
Thermal
Energy kinetic energy
associated with random molecular motion;
intensive property
Calorie (cal) the quantity of heat required
to change the temperature of one gram of
water by one degree Celsius
Joule (J) SI unit for heat
Chemical systems tend toward a state of
minimum potential energy and maximum
disorder.

If Hrxn < 0, reaction is exothermic (transfers


heat to the surroundings; feels hot)
If Hrxn > 0, reaction is endothermic
(absorbs heat from the surroundings; feels
cold)
Enthalpy is an extensive property.
Hrxn = Hproducts - Hreactants
Four ways to find Hrxn:
1.
2.
3.
4.

Hesss Law
By Hf
Bond energies
Calorimetry

Calorimetry measure of heat flow (using


calorimeter)
Heat capacity J/mol C
Specific heat J/g C
Four formulas to remember in
Calorimetry:
1.
2.
3.
4.

qsystem+ qsurroundings = 0
q = m x C x T
qrxn=Hrxnnlimiting reactant
qcal=CcalT

State function: depends only on the initial


and final states of system, not on how the
internal energy is used.

Thermochemical equations are balanced


chemical reaction plus the H value for the
reaction.

Law of Conservation of Energy (First


Law of Thermodynamics) energy is
neither created nor destroyed in chemical
reactions and physical changes

The standard enthalpy of formation of a


pure element in its reference state is 0.

The energy of an isolated system is


constant.
1 cal = 4.184 Joules

Hesss Law

Enthalpy Change, H, is the change in


heat content at constant pressure.

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Hesss Law of Heat Summation states


that the enthalpy change for a reaction is
the same whether it occurs by one step or
by any (hypothetical) series of steps.

Hrxn = n Hf products - n Hf reactants

Literary Archives Committee

Thermochemistry

Chem 16

nd

Long Exam Reviewer

April 2015

Bond Energies

Gibbs Free Energy

Bond energy is the amount of energy


required to break the bond and separate the
atoms in the gas phase.

G = H - TS (at constant T &P)

To break a bond always requires and


absorption of energy.
How to use this method in determining
Hrxn?
Determine how many bonds are there in a
compound, determine if the reaction
requires absorption/release of energy then
add.

Sign conventions for G


- G > 0 reaction is nonspontaneous
- G = 0 system is at equilibrium
- G < 0 reaction is spontaneous
Changes in free energy
G298 = nGproducts - nGreactants

Hrxn = n Hf products - n Hf reactants


Work
W=-PV
H=E+PV
H=E+PV
The internal energy, E, is all of the energy
contained within a substance. The first law
of thermodynamics states that the change in
internal energy, E, is determined by the
heat flow, q, and the work, w.
E = q + w
E = Efinal Einitial = Eproducts - Ereactants
q>0 if heat is absorbed by the system
q<0 if heat is absorbed by the surroundings
w>0 if the surroundings do work on the
system
w<0 if the system does work on the
surroundings
Work is defined as force acting through a
specified distance.
w=Fxd=-PV=-(ngas)RT
R= 8.314 J / mol K

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Literary Archives Committee

Thermochemistry