I get a message like "File already opened by something else."
This is your code that I changed, and now it works for me:
StreamReader fileStream = new StreamReader (file name);
var doc = new XmlDocument ();
doc.Load ( FileStream );
var node = doc.SelectSingleNode (@ "config / webservices / webservice / value");
node.InnerText = TextBox1.Text;
fileStream.Close ();
doc.Save(_);