Your first error is – you need a certificate file. Or at least path to them, so that you can verify the OpenSSL.org certificate.
Your second error – you don’t specify a file and -CAfile requires a single certificate (PEM or DER encoded).
The easiest way to perform connection with OpenSSL.org:
Download mozilla certificate bundle from here: http://curl.haxx.se/docs/caextract.html
Run openssl s_client -connect www.openssl.org:443 -CAfile .\cabundle.crt and you should have a nice return code 0.
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