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'While' carries a sense of the duration of an activity or event, and often goes with the present participle of the following verb. 'When' may carry such a sense, but may also refer to a specific point in time.

Examples of 'while':

'She arrived while I was sweeping the floor.'

'Be careful while you are carrying that tray.'

'While you were singing, I went to the kitchen.'

'When' could replace 'while' in those examples, though it would be less natural.

Examples of 'when':

'She arrived when the TV programme had just started.'

'Be careful when you pick that knife up.'

'When you began to sing, I went to the kitchen.'

'While' could not replace 'when' in those examples.

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