Gibbs Free Energy

 What’s “free” about Gibbs free energy?

 The change in free energy for a process

equals the maximum work that can be done
by the system on the surroundings in a
spontaneous process occurring at constant
temperature and pressure.

DG = wmax
 Gibbs Free Energy

Example: What is the maximum work that can be

performed by the combustion of 25.0 g of
methanol (CH3OH)?

Step 1: Write a balanced equation.

 Gibbs Free Energy

Step 2: Calculate DGrxn

Step 3: Calculate the DG for the mass used

in the reaction.
 Gibbs Free Energy
 On your exam, you must be able to write a
balanced equation for a simple combustion
reaction (including predicting the products).

 You will then be expected to calculate the

maximum work that can be performed using a
given number of grams or moles of a reactant.
 Gibbs Free Energy

 You should be able to write a balanced equation

for the combustion of an organic compound or a
metal.

 Organic compounds:

CnHm + O2 CO2 + H2O

Not bal.
CxHYOn + O2 CO2 + H2O

 Metals:

Metal + O2 Metal oxide Not bal.

 Gibbs Free Energy
 You can use the signs (positive or negative) of
DH and DS to predict whether a reaction (or
process) will be:
 Spontaneous at all temperatures

 Spontaneous only at high temperatures

 Spontaneous only at low temperatures

 Non-spontaneous at all temperatures

 Gibbs Free Energy
 The sign of DG (and therefore the spontaneity
of the reaction) will depend on
 the sign of DH and DS
 relative magnitude of the enthalpy and the
entropy terms.
 In some cases, the temperature will impact
the spontaneity of a reaction.

DG = DH – TDS

DG = DH + (- TDS)
Enthalpy Entropy
term term
Gibbs Free Energy
Effect of Temperature of Spontaneity

DH DS DG Spontaneity
- + always - Spon. all T
+ - always + Non-spon. all T

- - - at low T spon. at low T

+ + - at high T spon. at high T

 Gibbs Free Energy

Example: Predict whether the following reaction

will be spontaneous at low temperature, high
temperature, at all temperatures or always non-
spontaneous.

2 PbS(s) + 3 O2 (g)  2 PbO (s) + 2 SO2 (g)

DH = neg.
DS = neg
 Gibbs Free Energy
Example: Given the standard heats of formation
below, predict whether the following reaction will
be spontaneous at low temperature, high
temperature, at all temperatures or always non-
spontaneous.

CaO (s) + 3 C (graphite)  CaC2 (s) + CO (g)

DHfo (CaO) = - 635.1 kJ/mol

DHfo (CaC2) = - 59.9 kJ/mol
DHfo (CO) = - 110.5 kJ/mol
Gibbs Free Energy
 Gibbs Free Energy
 For a system in which the reactants and/or
products are not present in their standard
states, the values of DG and DGo are related:

DG = DGo + RT lnQ

where DG = Gibbs free energy change

DGo = standard Gibbs free energy change
R = 8.314 J/mol.K
T = temp. in Kelvin
Q = reaction quotient
 Free Energy and Equilibrium Constants
 For a system at equilibrium,

 DG = 0
Q = K

 and the standard free energy change (DGo) for

the reaction is directly related to the
equilibrium constant for the reaction

DGo = -RT ln K
 Free Energy and Equilibrium Constants
 This equation can be used to calculate DGo for
a reaction when the equilibrium constant or the
equilibrium concentrations are known.

 The equation can also be rearranged and used

to find the value of the equilibrium constant if
DGo for the reaction is known:
o
K = e-DG /RT
 Free Energy and Equilibrium Constants
Example: Find DGo for the following reaction at
25oC if Kp = 7.00 x 105.

N2 (g) + 3 H2 (g) 2 NH3 (g)

 Free Energy and Equilibrium Constants
Example: Calculate the equilibrium constant at
25oC for the dissolution of barium fluoride if DGo
for this process is +32.9 kJ per mole of barium
fluoride.
Free Energy and Equilibrium Constants
 Free Energy and Equilibrium Constants
 Once you find the value for the equilibrium
constant, you can use the equilibrium constant
to :
 Calculate the equilibrium concentrations of
the products and/or reactants.

 How would you calculate the concentrations of

barium ions and fluoride ions present in a
saturated solution of barium fluoride?
Free Energy and Equilibrium Constants