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Reference of web service in .NET
http://msdn2.microsoft.com/en-us/library/aa480728.aspx#wsmsplat_topic2
Web services are based on a core set of standards that describe the syntax and semantics of software communication: XML provides the common syntax for representing data; the Simple Object Access Protocol (SOAP) provides the semantics for data exchange; and the Web Services Description Language (WSDL) provides a mechanism to describe the capabilities of a Web service. Additional specifications, collectively referred to as the WS-* architecture, define functionality for Web services discovery, eventing, attachments, security, reliable messaging, transactions, and management.
Web form link:
http://msdn2.microsoft.com/en-us/library/65tcbxz3(VS.71).aspx
Web Forms are the dynamic web interface to allow users to interacte with the web applications or web services.
The difference is web forms provided an interface layer for the users to use the web services. .Net also provided a rich library for web application programmers to build web forms. Web services involved the main program and the data interpretation and the web forms provided a user friendly interface to users who want to use the web services.