(Note I am the OP) **Master equation** The master equation can be written as: $$\frac{d p_n(t)}{dt}=\sum_{n'}\{W_{nn'}p_{n'}(t)-W_{n'n}p_n(t)\}$$ Where $p_n$ denotes the probability that the system is in state $n$ at time $t$. And $W_{nn'}\Delta t$ denotes the probability of the system changing from state $n'$ to the state $n$ in the time interval $\Delta t$. **Specific case** Let us say we have $n=1$ free enzyme, then: $$ \frac{dp_0(t)}{dt}=W_{01}p_1(t)$$ So what is $W_{01}$ this is the probability that the one enzyme is used up, let us call this $\mu$. $$\frac{dp_0(t)}{dt}=\mu p_1(t)$$ The average number of 'free enzymes' is given by: $$<n>=p_1(t)$$ Differentiating this gives: $$\frac{d<n>}{dt}=\frac{dp_1(t)}{dt}$$ But in our case, $$ \frac{dp_1(t)}{dt}=-\mu p_1(t)$$ Thus $$\frac{d<n>}{dt}=-\mu p_1(t)$$ $$\frac{d<n>}{dt}=-\mu<n>$$ From here with the assumption that $\mu\propto [S]$ you can follow through my derivation on [Biology.SE][1] **Sources** 1.'Stochastic processes in physics and chemistry' by N.G. Van Kampen chapter V 2. http://www.jpoffline.com/physics_docs/y4s7/advstatmech_ln.pdf [1]: http://biology.stackexchange.com/questions/38576/dwell-time-equations-for-atp-sythase?noredirect=1