Hi Sai Krishna,
I think your Shopping cart workflow is configured based on the product categories and departments.
That is the reason you have 3 approvals in the first line item, 2 approvals in the second line item.
Kindly check the 3rd line item Product category for the approvals even though the user IDs are mapped in Org structure in order to trigger the workflow for shopping cart line item.
Thanks,
Sravan