use this property
LabelToolTip="Volumes(in million)"
or
ToolTip="Volumes(in million)"
in your code
<asp:Series XValueMember="Days" YValueMembers="CashVolumn" ToolTip="Volumes(in million)"
IsValueShownAsLabel="true" LabelToolTip="Volumes(in million)" Name="Series1"
ChartType="Line" Color="Red" IsVisibleInLegend="true" BorderWidth="2">
</asp:Series>
<asp:Series Name="Series2" XValueMember="Days" YValueMembers="FTE" ToolTip="No of FTEs"
IsValueShownAsLabel="true" LabelToolTip="No of FTEs" ChartType="Line" YAxisType="Secondary"
IsVisibleInLegend="true" Color="BlueViolet" BorderWidth="2">
</asp:Series>