pdanes:
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...
When I open the file, it shows as plain text, and I must click on the 'XML' in
the status bar to open a syntax change dialog, in which XML is already
highlighted, and click OK to confirm that I really do want PsPad to use the
highlighting that I have prescribed. What am I doing wrong?
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If the file is a bit larger, the highlighter might not be activated
automatically.
You can try to increase the value in

Settings: Direct edit: 
[Special settings]
HLOnUpToSize=????

There are othere similar parameters, but the should not apply for XML.

hth,
  vbr

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