I am not sure what you are completely asking, but will take a try at giving you some steps.
I am going to assume you are using Periodic replication.
If you already have the RC Group you add volumes to that RC group, you have 2 ways to do that. If you are using the IMC: If the volume exists on the source side and destination side you simply add the source then the you will get a choice of compatible destination volumes on the target array. If the volume does NOT exist on the destination side you select the source volume then select NEW button and you can create the destination volume on the destination side and it will automatically be added to the RC group.
To keep them in sync when you created the Periodic RC group you had the option to select the period that you want them to sync. The array will sync at that interval. If you did not select an interval then you have to manually sync the RC group. Adding volumes to an existing RC group does not sync them right away, you have to wait until the next period of manually sync them the first time. IF you are using the IMC select the RC Group and right click and you will have an option to "Sync Remote Copy Groups"
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