I finally found a solution for my problem. In order to test my assembly I had created a Windows Form project which consumed the assembly. I noticed that in the bin\Debug folder for the WindowsFormApplication1 there was a WindowsFormApplication1.exe and with it was a WindowsFormApplication1.exe.config. So I copied that .config file to my PowerBuilder runtime directory and renamed it to <myapp>.exe.config. Now my PB application can call the assembly and the assembly can call the Web Service and everything works just fine!
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