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While such live online chat programs are mostly used by individuals for personal purposes, they can also be used for professional purposes.
For example, such live chat programs are used for global conferences by companies, especially the ones offered by instant messaging services.
Firstly, one should make sure that they take care of acting responsibly while the webcam is on.
Also, a webcam chat will have certain unscrupulous characters who would wish to lure you into doing something you wouldn't in normal circumstances.
Doing a search for these chat rooms will come up with a number of programs and websites which offer free live webcam chats.