hi, I look up in some books and find the following explanation for you . Hope it is helpful.
Because these two words are different in it's construction, there are some differences in the usage.
1.聊天 is a verb-subject word, so when it is used as verb predicate, it Cann't be followed any objects while 聊 has not this restriction;
eg. 我们聊天童年的往事。 X
我们聊了很多童年的往事。
2. 聊天 is a 离合词 (separable words), so when it is followed with tense particle or complements, the verb is usually separated from the object, while 聊 can be directly followed by the tense particle or complements.
eg. 我们聊了好久的天。
他们正在那聊着天。
我们正聊着。
我们聊了好久。
3. when a complement of state expressing how the actions is going on is used after, usually 聊 is used. not 聊天。
大家聊得开心极了。
if you want to use 聊天, you should repeat the v. by saying 大家聊天聊得开心极了。