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Is it safe to disconnect an external drive any time?

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MS Office, for instance, just LOVES to keep files open in unexpected places.
Whenever you open or save a file in MS Word, the program automatically starts using the same folder for its temporary files. So, if you start MS Word, creates two empty files, save and close one of the files to your external drive, then Word still keeps a temp file open in the same folder, stopping you from safely removing the device...