As you were told already, the needed output format is really bad and erronous. Nevertheless this can be done quite easily:
DECLARE @mockup TABLE(Empid INT,Empname VARCHAR(100),Salary DECIMAL(10,4),[Location] VARCHAR(100));
INSERT INTO @mockup VALUES(1,'Arul',100,'Chennai')
,(2,'One',200,'More');
SELECT 'Empid' AS [Column]
,EmpId AS [Value]
,'Empname' AS [Column]
,Empname AS [Value]
-- follow this pattern...
FROM @mockup t
FOR XML PATH('employee'),ROOT('root');
The result
<root>
<employee>
<Column>Empid</Column>
<Value>1</Value>
<Column>Empname</Column>
<Value>Arul</Value>
</employee>
<employee>
<Column>Empid</Column>
<Value>2</Value>
<Column>Empname</Column>
<Value>One</Value>
</employee>
</root>
But - by any chance - you should try to change this format. This is awful to query and will be your private headache for sure...
Some better suggestions:
<Employee>
<Column name="EmpId" value="1" />
<Column name="Empname" value="Arul" />
</Employee>
or
<employee id="1" name="Arul" />
or
<employee>
<Id>1</Id>
<Name>Arul</Name>
</employee>
or (if you really, really want to stick with this), at least a column index like here
<root>
<employee>
<Column inx="1">Empid</Column>
<Value inx="1">1</Value>
<Column inx="2">Empname</Column>
<Value inx="2">Arul</Value>
</employee>
<employee>
<Column inx="1">Empid</Column>
<Value inx="1">2</Value>
<Column inx="2">Empname</Column>
<Value inx="2">One</Value>
</employee>
</root>
The query for the last one is this
SELECT 1 AS [Column/@inx]
,'Empid' AS [Column]
,1 AS [Value/@inx]
,EmpId AS [Value]
,2 AS [Column/@inx]
,'Empname' AS [Column]
,2 AS [Value/@inx]
,Empname AS [Value]
-- follow this pattern...
FROM @mockup t
FOR XML PATH('employee'),ROOT('root');