Try this :
using System.Xml.Linq;
using System.Xml;
using System.Xml.XPath;
XDocument doc2 = XDocument.Parse(@"
<kml xmlns="http:
<placemark>
<name>Test</name>
<lookat>
<longitude>11111111111</longitude>
<latitude>1111111111111</latitude>
<altitude>500</altitude>
<range>500</range>
<tilt></tilt>
<heading>11111111</heading>
<altitudemode>relativeToGround</altitudemode>
</lookat>
<styleurl>#msn_ylw-pushpin70</styleurl>
<point>
<coordinates>111111111,1111111111</coordinates>
</point>
</placemark>
</kml>");
XmlNamespaceManager xnm = new XmlNamespaceManager(new NameTable());
xnm.AddNamespace("x", "http:
var longitude = doc2.XPathSelectElement("//x:longitude", xnm);
longitude.Value = "XXXXX";