Is there a way to limit the number of operators joining a chat session? 

By default,  this feature is not supported. If you need this feature, you can purchase operator client source code license and make a customization.

 

Also, if operators can not answer a chat request, is there a way to route the chat request to a different group for answering after a certain wait time?

 

Operator can select one customer, right click this customer, and then click "Transfer" to transfer customer to other operator.

 

Regards,

Eric