Suppose we have series of experiments, and we continue till event 1 occurs (with probability $p$, or the disjoint event 2 occurs (with probability $q$). If neither occurs (probability $1-p-q$) we throw again.
What is the probability that 1 occurs before 2? Call this probability $r$.
Now $r = P(\text {1 before 2}) = P(\text{1 before 2} | \text{first experiment event 1})P(\text{first experiment event 1}) + P(\text{1 before 2} | \text{first experiment event 2})P(\text{first experiment event 2}) + P(\text{1 before 2} | \text{first experiment not event 1 or event 2})P(\text{first experiment not event 1 or event 2})$.
Now this equals $1 \cdot p + 0 \cdot q + r(1-p-q)$, because if event 1 occurs in the first experiment, surely we have that 1 occurs before 2, and if event 2 occurs, it's certainly not the case that 1 occurs before 2, and if neither occurs, by independence of the experiments we have probability $r$ again, as we start over fresh.
So $r = p + r(1-p-q)$, so $(p+q)r = p$, or $r = \frac{p}{p+q}$.
Similarly we can reason that $P(\text {2 before 1}) = \frac{q}{p+q}$ and note that these sum to 1. So one of them happens, and the chances are in ratio to their respective success probabilities $p$ and $q$.
In your case $p = \frac{2}{16}, q = \frac{4}{16}$, so we get $\frac{1}{3}$ that sum 3 occurs before sum 5, and $\frac{2}{3}$ for the other way around.