You can use the email template variable only in the body of the emails. For modifying the email titles/subject lines you have to use the corresponding filter and add some custom code to a child themes functions.php file or via a custom plugin.
add_filter( 'woocommerce_email_subject_customer_processing_order', 'change_processing_email_subject', 1, 2 );
function change_processing_email_subject( $subject, $order ) {
global $woocommerce;
$blogname = wp_specialchars_decode(get_option('blogname'), ENT_QUOTES);
$subject = sprintf( 'Hi %s, thanks for your order on %s', $order->billing_first_name, $blogname );
return $subject;
}