Gobies are capable of changing sex both ways so adding a second may lead to a pair regardless of the sex of the fish you add. Generally the change from female to male goes faster and usually with less friction.
A possible way to sex Gobies would be by their genital papillas: the ones of females are generally thicker and more rounded at the end while male ones are generally thinner and rather taper to a point. It's best visible if the fish are well fed and have a full belly. It also helps to have a good number of specimen to compare.
Sent from my XT1254 using Tapatalk