Since SharePoint REST endpoint http://server/site/_api/
returns service reference and http://server/site/_api/web
returns an appropriate entry point ( SP.Web resource in this case) the specified requests are not identical.
For example, the request:
http://server/site/_api/web/title
will return SP.Web Title
property
but the request:
http://server/site/_api/title
will return the error:
Cannot find resource for the request title
From another hand, since _api/lists
is an alias to _api/web/lists
url, the following requests
http://server/site/_api/web/lists/getbytitle('Pages')
and
http://server/site/_api/lists/getbytitle('Pages')
will return the same SP.List resource.
References
Determine SharePoint REST service endpoint URIs