The file web.xml is also know as the deployment descriptor and is not tomcat-specific. If you want to find some documentation about the deployment descriptor look in the Java Servlet Specification, chapter 13 and also apendixes A and B. (this is for version 2.4, maybe you rather search for the most recent version, 3.1 I think)
Now if you are looking for documentation about the file web.xml in CATALINA_HOME/conf , the file itself is already well self-documented with internal comments, BTW, the first comment says:
<!-- This document defines default values for *all* web applications -->
<!-- loaded into this instance of Tomcat. As each application is -->
<!-- deployed, this file is processed, followed by the -->
<!-- "/WEB-INF/web.xml" deployment descriptor from your own -->
<!-- applications. -->
<!-- -->
<!-- WARNING: Do not configure application-specific resources here! -->
<!-- They should go in the "/WEB-INF/web.xml" file in your application. -->