Create the file ~/.config/gtk-3.0/gtk.css and add the following CSS rule:
toolbar separator {
background-color: #ff0000;
/* to make the separator thicker you can add a right border */
border-right: 2px solid #ff0000;
}
The above was tested on my Xfce system, I’m not sure if it will work in KDE. If it doesn’t work, copy the CSS rule at the bottom of the file you mentioned /usr/share/themes/Breath/gtk-3.0/gtk.css.
A logout/login will be needed to see the result in the Gtk theme.