Different points:
WEB Application:
1: Request to the Web application, usually directly return HTML or image data and so on.
2: The results from the Web application are typically displayed directly to the user via the Web browser.
Web Service:
1: The request to the Web service, generally return is Xml,json.
2: The data from the Web service is the original structure, usually not directly displayed to the user.
The role of 3:web service is generally to provide some services and interfaces for WEB application.
Same point:
1: all use HTTP to transmit data
2: All use HTTP authentication/authorization function to ensure data security.
3: Typically hosted on a Web server.
Thus, the main difference between the two is who they are dealing with, and web Service is typically interacting with Web application, while Web application is typically interacting with web browser. (Very similar to database and database application).