What is the ruling on performing voluntary prayers during official working hours?

All perfect praise be to Allah, The Lord of The Worlds, and may His Peace and Blessings be upon our Prophet Muhammad and upon all of his family and companions

There is no harm if  there was break time during official working hours, but if not then it is impermissible. And Allah Knows Best.

Is it permissible for a wife to give her money to her family as a charity, or a gift without asking her husband, or seeking his consent?

The wife has the right to give her money as a charity, or a gift to her family, or to other people after consulting her husband out of respect, and this is the meaning of treating on footing of kindness and equity. Therefore, if he wanted to stop her from helping her family, then there is no harm in not telling him.

Is it permissible for a Muslim physician to specialize in gynecology obstetrics, and what is the ruling on working as such?

Some fields of knowledge are an individual duty while others are a collective one, and specializing in gynecology obstetrics is a collective duty. However, if there were female physicians to treat women, then there is no need for a male gynecology obstetrics specialist to look at women`s Awrahs (private parts) except in necessary situations since the jurisprudential maxim says:” Necessity must only be assessed and answered proportionately.” And Allah Knows Best.

Is it permissible for a wife to leave her house without obtaining the permission of her husband, and not to come back unless he divorces her co-wife?

It is forbidden for the wife to leave without obtaining her husband`s permission, and it is impermissible for her to ask him to divorce her co-wife as this inflicts harm on the latter and such an act is forbidden in Islamic law.