Module

php -i

openssl

OpenSSL support => enabled
OpenSSL Library Version => OpenSSL 1.0.1e-fips 11 Feb 2013
OpenSSL Header Version => OpenSSL 1.0.1e-fips 11 Feb 2013
Openssl default config => /etc/pki/tls/openssl.cnf

Directive => Local Value => Master Value
openssl.cafile => no value => no value
openssl.capath => no value => no value

php.ini

[openssl]
; Most users should not specify a value for this directive as PHP will attempt to use the
; OS-managed cert stores in its absence. If specified, this value may still
; be overridden on a per-stream basis via the "cafile" SSL stream context option.
openssl.cafile =
openssl.capath =

Check Setting By Code

var_dump(openssl_get_cert_locations());

array(8) {
  ["default_cert_file"]=>
  string(21) "/etc/pki/tls/cert.pem"
  ["default_cert_file_env"]=>
  string(13) "SSL_CERT_FILE"
  ["default_cert_dir"]=>
  string(18) "/etc/pki/tls/certs"
  ["default_cert_dir_env"]=>
  string(12) "SSL_CERT_DIR"
  ["default_private_dir"]=>
  string(20) "/etc/pki/tls/private"
  ["default_default_cert_area"]=>
  string(12) "/etc/pki/tls"
  ["ini_cafile"]=>
  string(0) ""
  ["ini_capath"]=>
  string(0) ""
}

php -r 'print_r(openssl_get_cert_locations()["default_cert_file"]);'

/etc/pki/tls/cert.pem