The connectionString section gives strongly typed access to the connection strings through the ConfigurationManager class.
To read values from Connection strings
AppSettings is meant to store general/custom settings
To read values from AppSettings
Though we can however store the values of database connections in AppSettings, but if you observe properly, you can find out that there is a specific element (providerName="System.Data.SqlClient") for it in connectionStrings
But app settings is only key-value pair type.
Please let us know if this clears the doubt.
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