Equilibrium

• Equilibrium Constant, K (or Keq) describes

conditions AT equilibrium

 [ products ] n

K i

i
[ reactants ] n
 Equilibrium/ Reversibility

• Anything at equilibrium is theoretically

undergoing forward and reverse reactions:
• A+B↔C
– A + B  C AND C  A +B
• Equilibrium has 2 criteria:
– Reaction does not appreciably change in time
– Perturbation of that equilibrium will result in a
return to the equilibrium
 Assessing equilibrium
 [ products ] n
 [ products ]n

K i
Q i

 [reactants ] n
 [reactants ] n

i i

Q  reaction quotient, aka Ion Activity Product

(IAP) is calculated from knowing activity of all
components of a reaction
K  aka Keq, we get from thermodynamic data – it
is one number defined AT EQUILIBRIUM
Equilibrium for any reaction is when Q = K
Equations can be ‘added’ together, equilibrium constants also get
‘added’ together!

Convenient way to rewrite reactions (to look at more appropriate

reactions or to use things you’ve more directly measured….)

log Keq
• CaCO3(calcite) = Ca2+ + CO32- -8.48
• CO2(g) + H2O = H2CO30 -1.47
• H2CO30 = H+ + HCO3- -6.35
• H+ + CO32- = HCO3- +10.33

CaCO3(calcite) + CO2(g) + H2O = Ca2+ + 2 HCO3- -5.97

 Where do K’s come from?
• Measure directly – experimental
determination of conditions at equilibrium

• Use thermodynamic data – K is directly

related to free energy of reaction – GR
 Hydroxylapatite
• Ca5(PO4)3(OH) = OH- + 3 PO43- + 5 Ca2+

• Log K = -59.0351 at 25ºC

 Thermodynamics
• “the branch of science that deals with
energy levels and the transfer of energy
between systems and between different
states of matter”
 Thermodynamics
• Thermodynamics answers the following question:
• For any reaction - defined by a set of reactants
and products set in exactly defined conditions
(temperature, pressure, concentration, etc.)  will
that reaction go forward spontaneously or not??

• It can address ANY geochemical reaction, if

thermo says NO, rest assured the reaction will not
proceed, if thermo says yes, then we can progress
to the next question  how fast?
 What is Energy???
• “It is important to realize that in physics today, we have no
knowledge of what energy is. We do not have a picture that
energy comes in little blobs of a definite amount. It is not that
way.” –Richard Feynman

• HOWEVER  Feynman goes on to elaborate that energy has

meaning as a way to define, and quantify, changes which bring
about changes – between systems, energy levels, or states of
matter – i.e. for any reaction

• “How seriously must we take the physical existence of this

energy? No more and no less than any other bookkeeping
practices.” –Richard Feynman