I use the following code to initialize encryption...
Dim symmetricKey As New System.Security.Cryptography.RijndaelManaged()
With symmetricKey
.Key = Enc
PKCS7 padding and PKCS5 padding are the same thing. In this context they are synonyms.
EDIT:
The PKCS#7 padding is described in the PKCS#7 spec in section 10.3. PKCS#5 padding is described in the PKCS#5 spec in section 6.1.1 step 4. As you can see by examination, the padding algorithms are identical.