In: Chemistry
The ΔG°' for the reaction ATP + H2O
<----- ADP + Pi + H+ is -30.5 kJ
mol-1. Other organophosphate species also undergo
hydrolysis of the phosphate moiety via a similar reaction.
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Consider the following reaction that is not spontaneous when the
concentrations of the reactants and products are all 1 M.
ATP + Acetic acid <----- ADP + Acetyl
phosphate
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What concentration of acetic acid would be necessary to make the
reaction just begin to be spontaneous? (All other species in the
reaction remain at 1 M concentration. The temperature is T
= 25 °C. The hydrolysis reaction for acetyl phosphate is Acetyl
phosphate + H2O <------ Acetic acid + Pi +
H+; ΔG°' = -42.2 kJ mol-1.)
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[acetic acid] = _____M
Ans. Given, the standard free energy change of phosphate hydrolysis for-
ATP + H2O ------> ADP + Pi ; dG0’ = -30.5 kJ/ mol - Reaction 1
Ace-P + H2O ----> Acetic acid + Pi + H+ ; dG0’ = -61.9 kJ/ mol - Reaction 2
# When a reaction is reversed, the sign of standard free energy change is also reversed.
So,
Acetic acid + Pi + H+ ------> Ace-P + H2O ; dG0’ = +42.2 kJ/mol - Reaction 3
#. The net coupled reaction for the formation of acetyl phosphate (Ace-P) can be written as follow-
Acetic acid + Pi + H+ ---> Ace-P + H2O ; dG0’ = +42.2 kJ/mol ; Reaction 3
ATP + H2O ------> ADP + Pi ; dG0’ = -30.5 kJ/ mol ; Reaction 1
Net coupled Rxn: ATP + Acetic acid + H+ ---------> Ace-P + ADP ; dG0’net = ?
The dG0’ for the net coupled reaction is given by-
dG0’net = dG0’ of Rxn 3 + dG0’ of Rxn 1
Or, dG0’net = 42.2 kJ/mol + (-30.5 kJ/mol) = +11.7 kJ/mol
# Hence, dG0’ for the (net) reaction = +11.7 kJ / mol
# Calculating desired [acetic acid]:
# Using the equation dG0’ = - RT lnKeq - equation 1
Where, dG0’ = standard/ theoretical free energy change
T = temperature in kelvin = (0C + 273.15) K
Keq = equilibrium constant under given condition
R = 0.0083146 kJ mol-1 K-1
#Let the [acetic acid] = X M , while all other concentrations remain constant at 1.0 M.
ATP + Acetic acid + H+ ---------> Ace-P + ADP
Equilibrium constant for the reaction, Keq = [Ace-P] [ADP] / ([ATP] [acetic acid] [H+])
Or, Keq = 1/ X
Putting the value of Keq in equation 1-
11.7 kJ mol-1 K-1 = - (0.0083146 kJ mol-1 K-1) x 298.15K x ln (1/X)
Or, (11.7 kJ mol-1 K-1) / (2.479 kJ mol-1 K-1) = 2.303 log (1/X)
Or, 4.72 / 2.303 = log (1/X)
Or, (1/X) = antilog (2.05)
Or, (1/X) = 112.202
Or, X = 1 / 112.202
Hence, X = 0.0089
Therefore, required [Acetic acid] = X M = 0.0098 M