1) Place a shortcut of GTalk in the Desktop.
2) Right Click it, then goto Properties, then goto Shortcut tab.
3) Here you can see a text box named "Target".Here you can see the main installation path of GTalk within double quote(" ").
4) Then at the end you give a blank space after the double qoute, and write /nomutex in that text box.
5) Now click Ok to save.
Now you can open multiple GTalk window from those you can login with different users.
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